U.S. patent application number 13/962982 was filed with the patent office on 2015-02-12 for methods for controlling dual catalyst olefin polymerizations with an alcohol compound.
This patent application is currently assigned to Chevron Phillips Chemical Company LP. The applicant listed for this patent is Chevron Phillips Chemical Company LP. Invention is credited to Tony R. Crain, Ted H. Cymbaluk, Albert P. Masino, Max P. McDaniel, John D. Stewart, Qing Yang.
Application Number | 20150045521 13/962982 |
Document ID | / |
Family ID | 51390222 |
Filed Date | 2015-02-12 |
United States Patent
Application |
20150045521 |
Kind Code |
A1 |
Yang; Qing ; et al. |
February 12, 2015 |
Methods for Controlling Dual Catalyst Olefin Polymerizations With
An Alcohol Compound
Abstract
Methods for controlling properties of an olefin polymer using an
alcohol compound are disclosed. The MI and the HLMI of the polymer
can be decreased, and the Mw and the Mz of the polymer can be
increased, via the addition of the alcohol compound.
Inventors: |
Yang; Qing; (Bartlesville,
OK) ; McDaniel; Max P.; (Bartlesville, OK) ;
Crain; Tony R.; (Niotaze, KS) ; Masino; Albert
P.; (Tulsa, OK) ; Cymbaluk; Ted H.; (Seabrook,
TX) ; Stewart; John D.; (Friendswood, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron Phillips Chemical Company LP |
The Woodlands |
TX |
US |
|
|
Assignee: |
Chevron Phillips Chemical Company
LP
The Woodlands
TX
|
Family ID: |
51390222 |
Appl. No.: |
13/962982 |
Filed: |
August 9, 2013 |
Current U.S.
Class: |
526/64 ; 526/156;
526/212 |
Current CPC
Class: |
C08F 4/65916 20130101;
C08F 4/76 20130101; C08L 23/0815 20130101; C08F 210/14 20130101;
C08F 210/16 20130101; C08F 4/649 20130101; C08F 210/16 20130101;
C08F 210/16 20130101; C08F 210/16 20130101; C08F 2/01 20130101;
C08F 4/65904 20130101; C08F 2500/04 20130101; C08F 4/52 20130101;
C08F 210/16 20130101; Y10S 526/943 20130101; C08F 4/65904 20130101;
C08F 210/16 20130101; C08F 2410/01 20130101; C08F 2500/12 20130101;
C08F 4/65925 20130101; C08F 2/38 20130101; C08F 210/14 20130101;
C08F 2500/05 20130101; C08F 4/65927 20130101 |
Class at
Publication: |
526/64 ; 526/212;
526/156 |
International
Class: |
C08F 210/14 20060101
C08F210/14 |
Claims
1. A method of controlling a polymerization reaction in a
polymerization reactor system, the method comprising: (i)
contacting a dual catalyst system with an olefin monomer and an
optional olefin comonomer in the polymerization reactor system
under polymerization conditions to produce an olefin polymer,
wherein the dual catalyst system comprises a first metallocene
catalyst component, a second metallocene catalyst component, an
activator, and a co-catalyst; and (ii) introducing an amount of an
alcohol compound into the polymerization reactor system to (I)
reduce a melt index parameter of the olefin polymer; (II) increase
a molecular weight parameter of the olefin polymer selected from
Mw, Mz, or both; or (III) reduce a melt index parameter of the
olefin polymer and increase a molecular weight parameter of the
olefin polymer selected from Mw, Mz, or both.
2. The method of claim 1, wherein the alcohol compound comprises
methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
octanol, decanol, hexadecanol, cyclohexanol, phenol, benzyl
alcohol, or a combination thereof.
3. The method of claim 1, wherein the dual catalyst system
comprises: a first metallocene catalyst component comprising an
unbridged metallocene compound containing zirconium; a second
metallocene catalyst component comprising a bridged metallocene
compound containing zirconium or hafnium; an activator comprising
an activator-support, an aluminoxane compound, an organoboron or
organoborate compound, an ionizing ionic compound, or any
combination thereof; and a co-catalyst comprising an organoaluminum
compound.
4. The method of claim 3, wherein: the activator comprises an
activator-support comprising a fluorided solid oxide, a sulfated
solid oxide, or a combination thereof; the amount of the alcohol
compound introduced into the polymerization reactor system is in a
range from about 1:10,000 to about 1:10, based on the moles of
hydroxyl (--OH) groups of the alcohol compound to the weight of the
activator-support in grams added to the polymerization reactor
system; and the alcohol compound comprises a C.sub.1 to C.sub.12
hydrocarbyl alcohol.
5. The method of claim 1, wherein the polymerization reactor system
comprises a slurry reactor, a gas-phase reactor, a solution
reactor, or a combination thereof.
6. The method of claim 1, wherein the polymerization reactor system
comprises a single reactor.
7. The method of claim 1, wherein the olefin monomer comprises
ethylene and the olefin comonomer comprises a C.sub.3-C.sub.10
alpha-olefin.
8. The method of claim 1, further comprising: determining a MI, and
adjusting the amount of the alcohol compound introduced into the
polymerization reactor system based on the difference between the
determined MI and a target MI; determining a HLMI, and adjusting
the amount of the alcohol compound introduced into the
polymerization reactor system based on the difference between the
determined HLMI and a target HLMI; determining the Mw, and
adjusting the amount of the alcohol compound introduced into the
polymerization reactor system based on the difference between the
determined Mw and a target Mw; or determining the Mz, and adjusting
the amount of the alcohol compound introduced into the
polymerization reactor system based on the difference between the
determined Mz and a target Mz; or any combination thereof.
9. The method of claim 1, wherein: a weight ratio of the first
metallocene catalyst component to the second metallocene catalyst
component is in a range of from about 1:10 to about 10:1; and a
weight ratio of the first metallocene catalyst component to the
second metallocene catalyst component is substantially
constant.
10. The method of claim 1, wherein: the co-catalyst comprises an
organoaluminum compound; and the amount of the alcohol compound
introduced into the polymerization reactor system is in a molar
ratio range of from about 0.1:1 to about 0.9:1, based on the moles
of hydroxyl (--OH) groups of the alcohol compound to the moles of
the organoaluminum compound added to the polymerization reactor
system.
11. The method of claim 1, wherein the amount of the alcohol
compound introduced into the polymerization reactor system is in a
molar ratio range of from about 10:1 to about 1000:1, based on the
ratio of the moles of hydroxyl (--OH) groups of the alcohol
compound to the total moles of the first metallocene catalyst
component and the second metallocene catalyst component added to
the polymerization reactor system.
12. The method of claim 1, further comprising: a step of adjusting
a weight ratio of the first metallocene catalyst component to the
second metallocene catalyst component; or a step of adding hydrogen
to the polymerization reactor system to adjust the molecular weight
parameter, the melt index parameter, or both the molecular weight
parameter and the melt index parameter; or both.
13. A process for producing an olefin polymer with a target melt
index parameter, a target molecular weight parameter, or a target
melt index parameter and a target molecular weight parameter, the
process comprising: (a) contacting a dual catalyst system with an
olefin monomer and an optional olefin comonomer in a polymerization
reactor system under polymerization conditions, wherein the dual
catalyst system comprises a first metallocene catalyst component, a
second metallocene catalyst component, an activator, and a
co-catalyst; and (b) controlling an amount of an alcohol compound
introduced into the polymerization reactor system to produce the
olefin polymer with the target melt index parameter, the target
molecular weight parameter, or the target melt index parameter and
the target molecular weight parameter; wherein: the melt index
parameter is MI, HLMI, or both; and the molecular weight parameter
is Mw, Mz, or both.
14. The process of claim 13, wherein the olefin polymer has: a melt
index (MI) of less than about 10 g/10 min; a number-average
molecular weight (Mn) in a range from about 5,000 to about 40,000
g/mol; a weight-average molecular weight (Mw) in a range from about
100,000 to about 600,000 g/mol; or a Mw/Mn ratio in a range from
about 10 to about 40; or any combination thereof.
15. The process of claim 14, wherein the alcohol compound comprises
a C.sub.1 to C.sub.8 alkyl alcohol, and the olefin polymer is an
ethylene/.alpha.-olefin copolymer.
16. The process of claim 13, wherein the MI and HLMI of the olefin
polymer decrease as the amount of the alcohol compound added to the
polymerization reactor system increases.
17. The process of claim 13, wherein the Mw and Mz of the olefin
polymer increase as the amount of the alcohol compound added to the
polymerization reactor system increases.
18. The process of claim 13, wherein the olefin polymer comprises a
higher molecular weight component and a lower molecular weight
component, and wherein: a weight ratio of the higher molecular
weight component to the lower molecular weight component increases
as the amount of the alcohol compound added to the polymerization
reactor system increases; a peak molecular weight of the lower
molecular weight component is substantially unchanged as the amount
of the alcohol compound added to the polymerization reactor system
increases; or a peak molecular weight of the higher molecular
weight component is substantially unchanged as the amount of the
alcohol compound added to the polymerization reactor system
increases; or any combination thereof.
19. The process of claim 13, wherein: the polymerization reactor
system comprises a loop slurry reactor; the alcohol compound
comprises isopropyl alcohol; and the olefin polymer is an
ethylene/1-hexene copolymer.
20. The process of claim 19, wherein the dual catalyst system
comprises: a first metallocene catalyst component comprising an
unbridged metallocene compound containing zirconium; a second
metallocene catalyst component comprising a bridged metallocene
compound containing zirconium or hafnium; an activator-support
comprising a solid oxide treated with an electron-withdrawing
anion; and an organoaluminum compound.
Description
BACKGROUND OF THE INVENTION
[0001] There are various methods that can be employed to adjust or
control the melt flow properties and the molecular weight
characteristics of an olefin-based polymer produced using a dual
metallocene catalyst system. For instance, the catalyst composition
and the polymerization reaction conditions can be changed to vary
the melt flow properties and the molecular weight characteristics
of the polymer that is produced. However, additional methods of
adjusting or controlling the polymer properties are needed which do
not require changes in the catalyst composition or the
polymerization conditions. Accordingly, it is to this end that the
present disclosure is directed.
SUMMARY OF THE INVENTION
[0002] This summary is provided to introduce a selection of
concepts in a simplified form that are further described below in
the detailed description. This summary is not intended to identify
required or essential features of the claimed subject matter. Nor
is this summary intended to be used to limit the scope of the
claimed subject matter.
[0003] Various processes and methods related to the control of dual
catalyst olefin polymerizations are disclosed herein. In one
embodiment, a method of controlling a polymerization reaction in a
polymerization reactor system is provided herein, and in this
embodiment, the method can comprise:
[0004] (i) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in the polymerization reactor
system under polymerization conditions to produce an olefin
polymer,
[0005] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0006] (ii) introducing an amount of an alcohol compound into the
polymerization reactor system to reduce a melt index parameter
(e.g., melt index (MI), high load melt index (HLMI), etc.) of the
olefin polymer, to increase a molecular weight parameter (e.g.,
weight-average molecular weight (Mw), z-average molecular weight
(Mz), etc.) of the olefin polymer, or to reduce a melt index
parameter and increase a molecular weight parameter of the olefin
polymer.
[0007] A process for producing an olefin polymer with a target melt
index parameter (e.g., MI, HLMI, etc.), a target molecular weight
parameter (e.g., Mw, Mz, etc.), or a target melt index parameter
and a target molecular weight parameter, is provided herein, and in
this embodiment, the process can comprise:
[0008] (a) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in a polymerization reactor system
under polymerization conditions,
[0009] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0010] (b) controlling an amount of an alcohol compound introduced
into the polymerization reactor system to produce the olefin
polymer with the target melt index parameter (e.g., MI, HLMI,
etc.), the target molecular weight parameter (e.g., Mw, Mz, etc.),
or the target melt index parameter and the target molecular weight
parameter.
[0011] In these methods and processes, the melt index parameters,
such as MI and HLMI, of the olefin polymer can decrease as the
amount of the alcohol compound added to the polymerization reactor
system is increased. Further, the molecular weight parameters, such
as Mw and Mz, of the olefin polymer can increase as the amount of
the alcohol compound added to the polymerization reactor system is
increased.
[0012] Both the foregoing summary and the following detailed
description provide examples and are explanatory only. Accordingly,
the foregoing summary and the following detailed description should
not be considered to be restrictive. Further, features or
variations may be provided in addition to those set forth herein.
For example, certain embodiments may be directed to various feature
combinations and sub-combinations described in the detailed
description.
BRIEF DESCRIPTION OF THE FIGURE
[0013] The FIGURE presents a plot of the molecular weight
distribution as a function of the amount of isopropanol for
Examples 1-4.
DEFINITIONS
[0014] To define more clearly the terms used herein, the following
definitions are provided. Unless otherwise indicated, the following
definitions are applicable to this disclosure. If a term is used in
this disclosure but is not specifically defined herein, the
definition from the IUPAC Compendium of Chemical Terminology,
2.sup.nd Ed (1997), can be applied, as long as that definition does
not conflict with any other disclosure or definition applied
herein, or render indefinite or non-enabled any claim to which that
definition is applied. To the extent that any definition or usage
provided by any document incorporated herein by reference conflicts
with the definition or usage provided herein, the definition or
usage provided herein controls.
[0015] While compositions and methods are often described in terms
of "comprising" various components or steps, the compositions and
methods can also "consist essentially of" or "consist of" the
various components or steps, unless stated otherwise.
[0016] The terms "a," "an," and "the" are intended to include
plural alternatives, e.g., at least one. For instance, the
disclosure of "an activator," "an olefin comonomer," etc., is meant
to encompass one, or mixtures or combinations of more than one,
activator, olefin comonomer, etc., unless otherwise specified.
[0017] For any particular compound or group disclosed herein, any
name or structure (general or specific) presented is intended to
encompass all conformational isomers, regioisomers, stereoisomers,
and mixtures thereof that can arise from a particular set of
substituents, unless otherwise specified. The name or structure
(general or specific) also encompasses all enantiomers,
diastereomers, and other optical isomers (if there are any) whether
in enantiomeric or racemic forms, as well as mixtures of
stereoisomers, as would be recognized by a skilled artisan, unless
otherwise specified. A general reference to pentane, for example,
includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and a
general reference to a butyl group includes a n-butyl group, a
sec-butyl group, an iso-butyl group, and a t-butyl group.
[0018] Also, unless otherwise specified, any carbon-containing
group or compound for which the number of carbon atoms is not
specified can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, or 20 carbon atoms, or any range or combination
of ranges between these values. For example, unless otherwise
specified, any carbon-containing group or compound can have from 1
to 20 carbon atoms, from 1 to 18 carbon atoms, from 1 to 12 carbon
atoms, from 1 to 8 carbon atoms, from 2 to 20 carbon atoms, from 2
to 12 carbon atoms, from 2 to 8 carbon atoms, or from 2 to 6 carbon
atoms, and the like. Moreover, other identifiers or qualifying
terms can be utilized to indicate the presence of, or absence of, a
particular substituent, a particular regiochemistry, or
stereochemistry, or the presence or absence of a branched
underlying structure or backbone. Any specific carbon-containing
group is limited according to the chemical and structural
requirements for that specific group, as understood by one of
ordinary skill.
[0019] Other numerical ranges are disclosed herein. When Applicants
disclose or claim a range of any type, Applicants' intent is to
disclose or claim individually each possible number that such a
range could reasonably encompass, including end points of the range
as well as any sub-ranges and combinations of sub-ranges
encompassed therein, unless otherwise specified. As a
representative example, Applicants disclose that a weight ratio of
the higher molecular weight component to the lower molecular weight
component can be in a range from about 1:10 to about 10:1 in
certain embodiments. By a disclosure that the weight ratio of the
higher molecular weight component to the lower molecular weight
component can be in a range from about 1:10 to about 10:1,
Applicants intend to recite that the weight ratio can be any weight
ratio within the range and, for example, can be equal to about
1:10, about 1:9, about 1:8, about 1:7, about 1:6, about 1:5, about
1:4, about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, about
4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, or
about 10:1. Additionally, the weight ratio can be within any range
from about 1:10 to about 10:1 (for example, the weight ratio can be
in a range from about 1:2 to about 2:1), and this also includes any
combination of ranges between about 1:10 and 10:1. Likewise, all
other ranges disclosed herein should be interpreted in a manner
similar to these examples.
[0020] Applicants reserve the right to proviso out or exclude any
individual members of any such group, including any sub-ranges or
combinations of sub-ranges within the group, that can be claimed
according to a range or in any similar manner, if for any reason
Applicants choose to claim less than the full measure of the
disclosure, for example, to account for a reference that Applicants
may be unaware of at the time of the filing of the application.
Further, Applicants reserve the right to proviso out or exclude any
individual substituents, analogs, compounds, ligands, structures,
or groups thereof, or any members of a claimed group, if for any
reason Applicants choose to claim less than the full measure of the
disclosure, for example, to account for a reference that Applicants
may be unaware of at the time of the filing of the application.
[0021] The term "substituted" when used to describe a group or a
chain of carbon atoms, for example, when referring to a substituted
analog of a particular group or chain, is intended to describe or
group or chain wherein any non-hydrogen moiety formally replaces a
hydrogen in that group or chain, and is intended to be
non-limiting. A group or chain also can be referred to herein as
"unsubstituted" or by equivalent terms such as "non-substituted,"
which refers to the original group or chain. "Substituted" is
intended to be non-limiting and can include hydrocarbon
substituents as specified and as understood by one of ordinary
skill in the art.
[0022] The term "hydrocarbon" whenever used in this specification
and claims refers to a compound containing only carbon and
hydrogen. Other identifiers can be utilized to indicate the
presence of particular groups in the hydrocarbon (e.g., halogenated
hydrocarbon indicates the presence of one or more halogen atoms
replacing an equivalent number of hydrogen atoms in the
hydrocarbon). The term "hydrocarbyl group" is used herein in
accordance with the definition specified by IUPAC: a univalent
group formed by removing a hydrogen atom from a hydrocarbon (that
is, a group containing only carbon and hydrogen). Non-limiting
examples of hydrocarbyl groups include alkyl, alkenyl, aryl, and
aralkyl groups, among other groups as members.
[0023] The term "polymer" is used herein generically to include
olefin homopolymers, copolymers, terpolymers, and so forth. A
copolymer can be derived from an olefin monomer and one olefin
comonomer, while a terpolymer can be derived from an olefin monomer
and two olefin comonomers. Accordingly, "polymer" encompasses
copolymers, terpolymers, etc., derived from any olefin monomer and
comonomer(s) disclosed herein. Similarly, an ethylene polymer would
include ethylene homopolymers, ethylene copolymers, ethylene
terpolymers, and the like. As an example, an olefin copolymer, such
as an ethylene copolymer, can be derived from ethylene and a
comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer
and comonomer were ethylene and 1-hexene, respectively, the
resulting polymer can be categorized an as ethylene/1-hexene
copolymer. The term "polymer" also is meant to include all
molecular weight polymers, and is inclusive of lower molecular
weight polymers or oligomers. Applicants intend for the term
"polymer" to encompass oligomers derived from any olefin monomer
disclosed herein (as well from an olefin monomer and one olefin
comonomer, an olefin monomer and two olefin comonomers, and so
forth).
[0024] In like manner, the scope of the term "polymerization"
includes homopolymerization, copolymerization, terpolymerization,
etc., as well as processes that might also be referred to as
oligomerization processes. Therefore, a copolymerization process
can involve contacting an olefin monomer (e.g., ethylene) and an
olefin comonomer (e.g., 1-hexene) to produce an olefin
copolymer.
[0025] The terms "catalyst composition," "catalyst mixture,"
"catalyst system," and the like, do not depend upon the actual
product or composition resulting from the contact or reaction of
the initial components of the disclosed or claimed catalyst
composition/mixture/system, the nature of the active catalytic
site, or the fate of the co-catalyst, the metallocene compound(s),
any olefin monomer used to prepare a precontacted mixture, or the
activator (e.g., activator-support), after combining these
components. Therefore, the terms "catalyst composition," "catalyst
mixture," "catalyst system," and the like, encompass the initial
starting components of the composition, as well as whatever
product(s) may result from contacting these initial starting
components, and this is inclusive of both heterogeneous and
homogenous catalyst systems or compositions. The terms "catalyst
composition," "catalyst mixture," "catalyst system," and the like,
may be used interchangeably throughout this disclosure.
[0026] The terms "contact product," "contacting," and the like, are
used herein to describe compositions wherein the components are
contacted together in any order, in any manner, and for any length
of time. For example, the components can be contacted by blending
or mixing. Further, unless otherwise specified, the contacting of
any component can occur in the presence or absence of any other
component of the compositions described herein. Combining
additional materials or components can be done by any suitable
method. Further, the term "contact product" includes mixtures,
blends, solutions, slurries, reaction products, and the like, or
combinations thereof. Although "contact product" can, and often
does, include reaction products, it is not required for the
respective components to react with one another. Likewise,
"contacting" two or more components can result in a reaction
product or a reaction mixture. Consequently, depending upon the
circumstances, a "contact product" can be a mixture, a reaction
mixture, or a reaction product.
[0027] Although any methods and materials similar or equivalent to
those described herein can be used in the practice or testing of
the invention, the typical methods and materials are herein
described.
[0028] All publications and patents mentioned herein are
incorporated herein by reference for the purpose of describing and
disclosing, for example, the constructs and methodologies that are
described in the publications, which might be used in connection
with the presently described invention. The publications discussed
throughout the text are provided solely for their disclosure prior
to the filing date of the present application. Nothing herein is to
be construed as an admission that the inventors are not entitled to
antedate such disclosure by virtue of prior invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Disclosed herein are methods and processes directed to
controlling dual catalyst olefin polymerizations in a
polymerization reactor system via the addition of an alcohol
compound. In these methods and processes, the amount of the alcohol
compound added to the reactor system can be used to adjust a melt
index parameter (e.g., MI, HLMI, etc.) of the olefin polymer, and
additionally or alternatively, can be used to adjust a molecular
weight parameter (e.g., Mw, Mz, etc.) of the olefin polymer. The
polymerization reaction can be conducted in a reactor system which
can contain one reactor, or alternatively, two or more reactors in
series or parallel.
[0030] For example, in one embodiment, a method of controlling a
polymerization reaction in a polymerization reactor system is
disclosed. In this embodiment, the method can comprise:
[0031] (i) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in the polymerization reactor
system under polymerization conditions to produce an olefin
polymer,
[0032] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0033] (ii) introducing an amount of an alcohol compound into the
polymerization reactor system to (I) reduce a melt index parameter
(e.g., MI, HLMI, etc.) of the olefin polymer; (II) increase a
molecular weight parameter (e.g., Mw, Mz, etc.) of the olefin
polymer; or (III) reduce a melt index parameter and increase a
molecular weight parameter of the olefin polymer.
[0034] Thus, the addition of the alcohol compound (e.g., increasing
the amount of the alcohol compound) can decrease a melt index
parameter of the olefin polymer. Illustrative and non-limiting
examples of melt index parameters are MI (g/10 min, ASTM D1238,
190.degree. C., and 2.16 kg weight) and HLMI (g/10 min, ASTM D1238,
190.degree. C. and 21.6 kg weight). Additionally or alternatively,
the addition of the alcohol compound (e.g., increasing the amount
of the alcohol compound) can increase a molecular weight parameter
of the olefin polymer. Illustrative and non-limiting examples of
molecular weight parameters are Mw and Mz (in g/mol, determined
using gel permeation chromatography (GPC) or other suitable
analytical procedure).
[0035] In another embodiment, a process for producing an olefin
polymer with a target melt index parameter (e.g., MI, HLMI, etc.),
a target molecular weight parameter (e.g., Mw, Mz, etc.), or a
target melt index parameter and a target molecular weight
parameter, is disclosed. In this embodiment, the process can
comprise:
[0036] (a) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in a polymerization reactor system
under polymerization conditions,
[0037] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0038] (b) controlling an amount of an alcohol compound introduced
into the polymerization reactor system to produce the olefin
polymer with the target melt index parameter (e.g., MI, HLMI,
etc.), the target molecular weight parameter (e.g., Mw, Mz, etc.),
or the target melt index parameter and the target molecular weight
parameter.
[0039] Thus, the addition of the alcohol compound (e.g., increasing
the amount of the alcohol compound) can be used to produce an
olefin polymer with a target melt index parameter, or a target
molecular weight parameter, or both.
[0040] In these methods and processes, the alcohol compound can be
introduced (e.g., added, injected, etc.) into the polymerization
reactor system by any suitable means, for instance, alone, or with
a carrier (e.g., a carrier gas, a carrier liquid, etc.). The
alcohol compound can be introduced into the polymerization reactor
system at any suitable location within the reactor system. In one
embodiment, the alcohol compound can be added directly into a
polymerization reactor within the polymerization reactor system,
while in another embodiment, the alcohol compound can be introduced
into the polymerization reaction system at a feed or inlet location
other than directly into a polymerization reactor, for example, in
a recycle stream. In some embodiments, the alcohol compound can be
added to the reactor by itself, while in other embodiments, the
alcohol compound can be added to the reactor with a carrier or
solvent, non-limiting examples of which can include, but are not
limited to, isobutane, n-butane, n-pentane, isopentane, neopentane,
n-hexane, heptane, octane, cyclohexane, cycloheptane,
methylcyclohexane, methylcycloheptane, benzene, toluene, xylene,
ethylbenzene, and the like, or combinations thereof. In certain
embodiments, the alcohol compound can be added to the reactor with
an olefin monomer/comonomer, such as 1-butene, 1-hexene, or
1-octene, and the like. In particular embodiments contemplated
herein, the alcohol compound can be added to the polymerization
reactor system with the dual catalyst system. Additional feed
options for a polymerization reactor system are described in U.S.
Pat. No. 7,615,596, the disclosure of which is incorporated herein
by reference in its entirety.
[0041] Generally, the features of the methods and processes
disclosed herein (e.g., the dual catalyst system, the first
metallocene catalyst component, the second metallocene component,
the activator, the co-catalyst, the olefin monomer, the olefin
comonomer, the polymerization conditions, the polymerization
reactor system, the alcohol compound, the amount of the alcohol
compound, the melt index parameter, the molecular weight parameter,
among others) are independently described herein, and these
features can be combined in any combination to further describe the
disclosed processes and methods.
[0042] In certain methods and processes disclosed herein, a dual
catalyst system can be contacted with an olefin monomer and
optionally an olefin comonomer in the polymerization reactor
system, and an alcohol compound can be added to the reactor system.
As would be recognized by one of skill in the art, additional
components can be introduced into the polymerization reactor system
in addition to these recited components, and such unrecited
components are encompassed herein. For instance, in the operation
of a polymerization reactor system--depending, of course, on the
polymerization reactor type, the desired olefin polymer, etc.,
among other factors--solvents, diluents, fluidizing gases, recycle
streams, etc., also can be added or introduced into the
polymerization reactor and polymerization reactor system.
[0043] The weight ratio of the first metallocene catalyst component
to the second metallocene catalyst component in the dual catalyst
system generally is not limited to any particular range of weight
ratios. Nonetheless, in some embodiments, the weight ratio of the
first metallocene catalyst component to the second metallocene
catalyst component can be in a range of from about 1:100 to about
100:1, from about 1:50 to about 50:1, from about 1:25 to about
25:1, from about 1:10 to about 10:1, or from about 1:5 to about
5:1. Accordingly, suitable ranges for the weight ratio of the first
metallocene catalyst component to the second metallocene catalyst
component can include, but are not limited to, from about 1:15 to
about 15:1, from about 1:10 to about 10:1, from about 1:8 to about
8:1, from about 1:5 to about 5:1, from about 1:4 to about 4:1, from
about 1:3 to about 3:1, from about 1:2 to about 2:1, from about
1:1.8 to about 1.8:1, from about 1:1.5 to about 1.5:1, from about
1:1.3 to about 1.3:1, from about 1:1.25 to about 1.25:1, from about
1:1.2 to about 1.2:1, from about 1:1.15 to about 1.15:1, from about
1:1.1 to about 1.1:1, or from about 1:1.05 to about 1.05:1, and the
like.
[0044] Consistent with embodiments disclosed herein, the weight
ratio of the first metallocene catalyst component to the second
metallocene catalyst component can be held substantially constant
(e.g., within +/-5%), for example, for the production of a
particular polymer grade. In such circumstances, the addition of
the alcohol compound can be used to control, adjust, fine-tune,
etc., the production and properties of that particular polymer
grade, without having to vary the catalyst composition.
[0045] Optionally, if additional control parameters for the dual
catalyst polymerization process are desired other than the use of
an alcohol compound, the methods and processes disclosed herein can
further comprise a step of adjusting the weight ratio of the first
metallocene catalyst component to the second metallocene catalyst
component.
[0046] In some embodiments, the polymerization conditions can be
held substantially constant (e.g., within +/-5%), for example, for
the production of a particular polymer grade. Representative
polymerization conditions include absolute temperature, gauge
pressure, residence time, % solids, and the like. As above, in such
circumstances, the addition of the alcohol compound can be used to
control, adjust, fine-tune, etc., the production and properties of
that particular polymer grade.
[0047] Optionally, if additional control parameters for the dual
catalyst polymerization process are desired other than the use of
an alcohol compound, the methods and processes disclosed herein can
further comprise a step of adjusting at least one polymerization
condition (e.g., temperature, pressure, residence time, etc.).
[0048] Unexpectedly, in these methods and processes, melt index
parameters such as MI and HLMI of the olefin polymer can decrease
as the amount of the alcohol compound added to the polymerization
reactor system is increased. Also unexpectedly, molecular weight
parameters such as Mw and Mz of the olefin polymer can increase as
the amount of the alcohol compound added to the polymerization
reactor system is increased. The alcohol compound can be added to
the polymerization reactor system (e.g., into a polymerization
reactor) alone, with a carrier, with the dual catalyst system, etc.
The amount of the alcohol compound added to the reactor system is
not particularly limited, so long as the amount of the alcohol
compound added to the reactor system is sufficient to impact at
least one of the MI, HLMI, Mw, and Mz of the olefin polymer as
described herein, and does not adversely impact the catalyst
activity or polymer production rate in a significant manner (e.g.,
20%+ reduction in catalyst activity, polymer production rate, or
both). While not being limited thereto, the amount of the alcohol
compound added typically can be in a molar ratio range of moles of
hydroxyl (--OH) groups of the alcohol compound to the total moles
of the first metallocene catalyst component and the second
metallocene catalyst component from about 10:1 to about 1000:1.
This molar ratio is based on the respective amounts of hydroxyl
groups of the alcohol compound, the first metallocene catalyst
component, and the second metallocene catalyst component fed into
the reactor system (e.g., into a polymerization reactor). As a
non-limiting example of a 50:1 molar ratio, in a continuous
polymerization reactor system, the total amount of the first and
second metallocene catalyst components fed into the reactor(s) per
time interval can be "Y" moles/hour; thus, the amount of the
alcohol compound fed into the reactor(s) would be equal to "50 Y"
moles/hour (moles of hydroxyl groups) for a 50:1 molar ratio.
[0049] In some embodiments, this molar ratio (moles of hydroxyl
groups of the alcohol compound to total moles of metallocene
components) can be in a range from about 10:1 to about 1000:1, from
about 10:1 to about 750:1, from about 10:1 to about 500:1, from
about 20:1 to about 1000:1, from about 20:1 to about 750:1, from
about 20:1 to about 500:1, from about 20:1 to about 250:1, from
about 20:1 to about 200:1, or from about 20:1 to about 100:1. In
particular embodiments considered herein, the molar ratio can be in
a range from about 25:1 to about 1000:1, from about to about 25:1
to about 500:1, from about 25:1 to about 100:1, from about 50:1 to
about 1000:1, from about 100:1 to about 1000:1, or from about 50:1
to about 500:1.
[0050] Unexpectedly, in the disclosed methods and processes, the
ratio of Mz/Mw of the olefin polymer can decrease as the amount of
the alcohol compound added to the polymerization reactor system is
increased. However, also unexpectedly, the addition of the alcohol
compound can have substantially no effect on the Mn of the olefin
polymer. In this regard, "substantially" no effect (substantially
no change in Mn) means that the Mn after addition of the alcohol
compound is within +/-20% of the Mn prior to addition of the
alcohol compound. In some embodiments, the Mn can be within +/-10%
or, alternatively, +/-5%.
[0051] Moreover, in some embodiments, the step of introducing the
alcohol compound into the polymerization reactor system,
unexpectedly, can have substantially no effect (within +/-20%; in
some embodiments, within +/-10% or, alternatively, +/-5%) on the
activity of the dual catalyst system (or, for instance, can have
substantially no effect on the production rate of the olefin
polymer). As one of skill in the art would readily understand, an
excess of the alcohol compound, as compared to certain components
of the dual catalyst system, can drastically reduce the catalyst
activity and polymer production rate and, eventually, can "kill"
the reaction. Thus, the practical maximum amount of the alcohol
compound added to the polymerization reactor system is limited.
[0052] In an embodiment, the alcohol compound can be added into the
polymerization reactor system continuously. For instance, the
alcohol compound can be added to the reactor whenever the olefin
monomer or the metallocene catalyst components, or both, are added
to the reactor. Alternatively, the alcohol compound can be added
periodically, on an as-needed basis, or pulsed to the reactor.
Intermittent addition to a polymerization reactor is disclosed, for
instance, in U.S. Pat. No. 5,739,220 and U.S. Patent Publication
No. 2004/0059070, the disclosures of which are incorporated herein
by reference in their entirety.
[0053] The addition of the alcohol compound can be used to produce
olefin polymers having various melt flow rate and molecular weight
properties. For example, the MI of the olefin polymer (e.g., an
ethylene/.alpha.-olefin copolymer) can be less than about 50, less
than about 25, less than about 10, or less than about 5 g/10 min.
Contemplated ranges for the MI of olefin polymers produced by the
methods and processes disclosed herein can include, but are not
limited to, from 0 to about 25 g/10 min, from 0 to about 5 g/10
min, from 0 to about 1 g/10 min, from 0 to about 0.5 g/10 min, from
about 0.005 to about 5 g/10 min, from about 0.005 to about 2 g/10
min, from about 0.005 to about 1 g/10 min, from about 0.01 to about
20 g/10 min, from about 0.01 to about 2 g/10 min, from about 0.01
to about 1 g/10 min, from about 0.05 to about 15 g/10 min, from
about 0.05 to about 5 g/10 min, from about 0.05 to about 1 g/10
min, from about 0.05 to about 0.5 g/10 min, from about 0.1 to about
2 g/10 min, from about 0.1 to about 1 g/10 min, or from about 0.1
to about 0.8 g/10 min.
[0054] The HLMI of the olefin polymer produced can be, for example,
less than about 200, less than about 100, less than about 50, or
less than about 25 g/10 min. Contemplated ranges for the HLMI of
olefin polymers produced by the methods and processes disclosed
herein can include, but are not limited to, from 0 to about 100
g/10 min, from 0 to about 50 g/10 min, from 0 to about 25 g/10 min,
from 0 to about 20 g/10 min, from about 0.005 to about 100 g/10
min, from about 0.005 to about 50 g/10 min, from about 0.005 to
about 25 g/10 min, from about 0.01 to about 100 g/10 min, from
about 0.01 to about 75 g/10 min, from about 0.01 to about 10 g/10
min, from about 0.1 to about 50 g/10 min, from about 0.1 to about
20 g/10 min, from about 0.1 to about 15 g/10 min, from about 0.1 to
about 10 g/10 min, from about 0.5 to about 100 g/10 min, from about
0.5 to about 25 g/10 min, or from about 1 to about 15 g/10 min.
[0055] In some embodiments, the weight-average molecular weight
(Mw) of the olefin polymer produced by the methods and processes
disclosed herein can be in a range from about 70,000 to about
600,000 g/mol, from about 100,000 to about 600,000 g/mol, or from
about 100,000 to about 500,000 g/mol. In other embodiments, the Mw
can be in range from about 100,000 to about 400,000 g/mol, from
about 150,000 to about 475,000 g/mol, from about 200,000 to about
500,000 g/mol, from 200,000 to about 400,000 g/mol, from about
225,000 to about 400,000 g/mol, or from about 250,000 to about
450,000 g/mol. Suitable ranges for the number-average molecular
weight (Mn) of the olefin polymer can include, but are not limited
to, from about 5,000 to about 50,000 g/mol, from about 5,000 to
about 40,000 g/mol, from about 5,000 to about 30,000 g/mol, from
about 6,000 to about 25,000 g/mol, from about 6,000 to about 20,000
g/mol, from about 7,000 to about 30,000 g/mol, from about 8,000 to
about 25,000 g/mol, from about 9,000 to about 25,000 g/mol, or from
about 9,000 to about 22,000 g/mol. Further, suitable ranges for the
z-average molecular weight (Mz) of the olefin polymer can include,
but are not limited to, from about 700,000 to about 3,000,000
g/mol, from about 800,000 to about 3,000,000 g/mol, from about
1,000,000 to about 3,000,000 g/mol, from about 700,000 to about
2,500,000 g/mol, from about 800,000 to about 2,500,000 g/mol, from
about 1,000,000 to about 2,500,000 g/mol, from about 800,000 to
about 2,000,000 g/mol, or from about 1,000,000 to about 2,000,000
g/mol.
[0056] In some embodiments, the Mw/Mn ratio of the olefin polymer
produced by the methods and processes disclosed herein can be in a
range from about 5 to about 50, from about 5 to about 40, from
about 5 to about 35, from about 8 to about 30, from about 10 to
about 40, from about 10 to about 35, from about 12 to about 35,
from about 15 to about 35, from about 12 to about 40, from about 15
to about 30, from about 18 to about 30, from about 7 to about 45,
from about 8 to about 40, from about 9 to about 35, from about 10
to about 30, or from about 12 to about 28. Likewise, in some
embodiments, the Mz/Mw ratio of the olefin polymer can be in a
range from about 3 to about 7, from about 3 to about 6, from about
3 to about 5.5, from about 3.5 to about 7, from about 3.5 to about
6, from about 3.5 to about 5.5, from about 3.5 to about 5, from
about 3.8 to about 6.5, from about 3.8 to about 6, from about 3.8
to about 5.5, from about 3.8 to about 5.3, from about 3.8 to about
5, or from about 3.8 to about 4.8.
[0057] In one embodiment, no hydrogen is added to the
polymerization reactor system. As one of ordinary skill in the art
would recognize, hydrogen can be generated in-situ by the first
metallocene catalyst component, the second metallocene catalyst
component, or both catalyst components, during the dual catalyst
olefin polymerization process. In this embodiment, there is no
"added hydrogen" to the reactor system.
[0058] Although not required, however, hydrogen can be added to the
polymerization reactor system in certain embodiments. Optionally,
for instance, the methods and processes provided herein can further
comprise a step of adding hydrogen to the polymerization reactor
system to adjust the molecular weight parameter (e.g., Mw, Mz,
etc.) of the olefin polymer, to adjust the melt index parameter
(MI, HLMI, etc.) of the olefin polymer, or to adjust both the
molecular weight parameter and the melt index parameter of the
olefin polymer, if desired. Generally, the step of adding hydrogen
can decrease the Mw, decrease the Mz, increase the MI, or increase
the HLMI, or any combination thereof, of the polymer. Moreover, the
addition of hydrogen also can decrease the Mn of the polymer.
[0059] In embodiments where hydrogen is added to the polymerization
reactor system, the hydrogen addition can be held substantially
constant (e.g., within +/-20%), for example, for the production of
a particular polymer grade. For example, the ratio of hydrogen to
the olefin monomer in the polymerization process can be controlled,
often by the feed ratio of hydrogen to the olefin monomer entering
the reactor. Further, the addition of comonomer (or comonomers) can
be, and generally is, substantially constant throughout the
polymerization run for a particular copolymer grade. However, in
other embodiments, it is contemplated that monomer, comonomer (or
comonomers), or hydrogen, or combinations thereof, can be
periodically pulsed to the reactor, for instance, in a manner
similar to that employed in U.S. Pat. No. 5,739,220 and U.S. Patent
Publication No. 2004/0059070, the disclosures of which are
incorporated herein by reference in their entirety.
[0060] The olefin polymer produced using the dual catalyst system
can contain a higher molecular weight component and a lower
molecular weight component in certain embodiments disclosed herein.
The weight ratio of the higher molecular weight component to the
lower molecular weight component generally is not limited to any
particular range of weight ratios. Nonetheless, in some
embodiments, the weight ratio of the higher molecular weight
component to the lower molecular weight component can be in a range
of from about 1:100 to about 100:1, from about 1:50 to about 50:1,
from about 1:25 to about 25:1, from about 1:10 to about 10:1, or
from about 1:5 to about 5:1. Accordingly, suitable ranges for the
weight ratio of the higher molecular weight component to the lower
molecular weight component can include, but are not limited to,
from about 1:15 to about 15:1, from about 1:10 to about 10:1, from
about 1:8 to about 8:1, from about 1:5 to about 5:1, from about 1:4
to about 4:1, from about 1:3 to about 3:1, from about 1:2 to about
2:1, from about 1:1.8 to about 1.8:1, from about 1:1.5 to about
1.5:1, from about 1:1.3 to about 1.3:1, from about 1:1.25 to about
1.25:1, from about 1:1.2 to about 1.2:1, from about 1:1.15 to about
1.15:1, from about 1:1.1 to about 1.1:1, or from about 1:1.05 to
about 1.05:1, and the like.
[0061] In the disclosed methods and processes, the MI (or HLMI, or
both) of the olefin polymer can decrease, the Mw (or Mz, or both)
of the olefin polymer can increase, or both the melt index
parameter can decrease and the molecular weight parameter can
increase, as the amount of the alcohol compound added to the
polymerization reactor system is increased. For olefin polymers
having a higher molecular weight component and a lower molecular
weight component, unexpectedly, the introduction of the alcohol
compound into the polymerization reactor system can increase the
weight ratio of the higher molecular weight component to the lower
molecular weight component.
[0062] Moreover, the addition of the alcohol compound into the
polymerization reactor system can have substantially no effect on
the peak molecular weight (Mp) of the lower molecular weight
component of the olefin polymer. Additionally or alternatively, in
certain embodiments, the addition of the alcohol compound into the
polymerization reactor system can have substantially no effect on
the peak molecular weight (Mp) of the higher molecular weight
component of the olefin polymer. In this regard, "substantially" no
effect (substantially no change in Mp) means that the peak
molecular weight after addition of the alcohol compound is within
+/-20% of the peak molecular weight prior to addition of the
alcohol compound. In some embodiments, the peak molecular weights
can be within +/-10% or, alternatively, +/-5%.
[0063] For the production of a particular grade of an olefin
polymer, with certain desired polymer properties, a target MI (or
HLMI, or both) of the olefin polymer can be established. Thus, when
the particular polymer grade is produced, variables can be adjusted
in order to achieve the targeted MI (or HLMI, or both).
Accordingly, in some embodiments, the processes and methods
provided herein optionally can further comprise the steps of
determining (or measuring) the MI (or HLMI, or both) of the olefin
polymer, and then adjusting the amount of the alcohol compound
introduced into the polymerization reactor system based on the
difference between the measured MI (or HLMI, or both) and the
target MI (or HLMI, or both). As a representative example, if the
measured MI (or HLMI, or both) is higher than that of the target MI
(or HLMI, or both) for the production of a particular grade of
olefin polymer, then the alcohol compound can be added at an amount
appropriate to make the measured MI (or HLMI, both) equivalent to
that of the target MI (or HLMI, or both). For instance, the feed
rate of the alcohol compound can be increased to reduce the MI (or
HLMI, or both) of the olefin polymer.
[0064] Likewise, for the production of a particular grade of an
olefin polymer, with certain desired polymer properties, a target
Mw (or Mz, or both) of the olefin polymer can be established. Thus,
when the particular polymer grade is produced, variables can be
adjusted in order to achieve the targeted Mw (or Mz, or both).
Accordingly, in some embodiments, the processes and methods
provided herein optionally can further comprise the steps of
determining (or measuring) the Mw (or Mz, or both) of the olefin
polymer, and then adjusting the amount of the alcohol compound
introduced into the polymerization reactor system based on the
difference between the measured Mw (or Mz, or both) and the target
Mw (or Mz, or both). As a representative example, if the measured
Mw (or Mz, or both) is less than that of the target Mw (or Mz, or
both) for the production of a particular grade of olefin polymer,
then the alcohol compound can be added at an amount appropriate to
make the measured Mw (or Mz, or both) equivalent to that of the
target Mw (or Mz, or both). For instance, the feed rate of the
alcohol compound can be increased to increase the Mw (or Mz, or
both) of the olefin polymer.
[0065] Consistent with embodiments disclosed herein, optionally and
as-needed, various polymerization conditions or process variables
can be adjusted or controlled during the operation of a
polymerization reactor system, and such conditions or variables can
include, but are not limited to, reaction temperature, reactor
pressure, residence time, catalyst system flow rate into the
reactor, monomer flow rate (and comonomer, if employed) into the
reactor, olefin polymer output rate, recycle rate, hydrogen flow
rate (if employed), reactor cooling status, slurry density,
circulation pump power, and the like.
[0066] In each of the methods and process disclosed herein, the
melt index parameter (e.g., MI, HLMI) of the olefin polymer can
decrease, the molecular weight parameter (e.g., Mw, Mz) of the
olefin polymer can increase, or the melt index parameter can
decrease and the molecular weight parameter can increase, as the
amount of the alcohol compound added to the polymerization reactor
system increases.
Alcohol Compounds
[0067] Alcohol compounds suitable for use herein can include, for
example, mono-ols (monoalcohols), diols, triols, or polyols, as
well as combinations thereof. Moreover, suitable alcohol compounds
can be linear or branched, and can be a primary alcohol, a
secondary alcohol, or a tertiary alcohol. Typically, the alcohol
compound can comprise a hydrocarbyl alcohol, although this is not a
requirement. For instance, the alcohol compound can comprise an
alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an arylalkyl
alcohol, and the like, as well as combinations thereof.
[0068] The number of carbon atoms in the alcohol compound is not
particularly limited, although in some embodiments, the alcohol
compound can comprise a C.sub.1 to C.sub.32 alcohol; alternatively,
a C.sub.1 to C.sub.18 alcohol; alternatively, a C.sub.1 to C.sub.12
alcohol; alternatively, a C.sub.1 to C.sub.8 alcohol;
alternatively, a C.sub.1 to C.sub.4 alcohol; alternatively, a
C.sub.2 to C.sub.12 alcohol; or alternatively, a C.sub.2 to C.sub.6
alcohol. Representative and non-limiting examples of suitable
alcohol compounds (e.g., mono-ol compounds) can include the
following: methanol, ethanol, propanol (e.g., isopropanol,
n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol,
hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol,
phenol, benzyl alcohol, etc., as well as combinations thereof. In
one embodiment, the alcohol compound can comprise methanol,
ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g.,
n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol,
decanol, hexadecanol, and the like, or a combination thereof. In
another embodiment, the alcohol compound can comprise cyclohexanol,
phenol, benzyl alcohol, and the like, or a combination thereof. In
yet another embodiment, the alcohol compound can comprise methanol,
ethanol, propanol (e.g., isopropanol, n-propanol), butanol (e.g.,
n-butanol, isobutanol), pentanol, hexanol, heptanol, octanol, and
the like, or a combination thereof. In still another embodiment,
the alcohol compound can comprise methanol, ethanol, propanol
(e.g., isopropanol, n-propanol), butanol (e.g., n-butanol,
isobutanol), and the like, or a combination thereof, or
alternatively, ethanol, propanol (e.g., isopropanol, n-propanol),
butanol (e.g., n-butanol, isobutanol), and the like, or a
combination thereof.
[0069] In certain embodiments, the alcohol compound can comprise a
diol, illustrative examples of which can include, but are not
limited to, methanediol, ethylene glycol, propylene glycol,
butanediol (e.g., 1,4-butanediol), pentanediol, octanediol,
bisphenol A, and the like, as well as any combination thereof.
Accordingly, the alcohol compound can comprise ethylene glycol,
propylene glycol, or both, in some embodiments; alternatively,
methanediol; alternatively, ethylene glycol; alternatively,
propylene glycol; alternatively, butanediol (e.g., 1,4-butanediol);
alternatively, pentanediol; alternatively, octanediol; or
alternatively, bisphenol A.
[0070] In other embodiments, the alcohol compound can comprise a
triol, a polyol, or combinations thereof, illustrative examples of
which can include, but are not limited to, glycerol, benzenetriol,
erythritol, xylitol, mannitol, and the like, as well as
combinations thereof. Accordingly, the alcohol compound can
comprise glycerol in some embodiments; alternatively, benzenetriol;
alternatively, erythritol; alternatively, xylitol; or
alternatively, mannitol.
[0071] The alcohol compound, in accordance with an embodiment
disclosed herein, can have a boiling point of at least 60.degree.
C., such as, for example, a boiling point of at least 65.degree.
C., a boiling point of at least 70.degree. C., or a boiling point
of at least 85.degree. C. Alcohol compounds having boiling points
of at least 100.degree. C., or at least 150.degree. C., can be
employed as well. Yet, in another embodiment, the alcohol compound
can have a boiling point in the 60.degree. C. to 400.degree. C.
range; alternatively, a boiling point in the 60.degree. C. to
350.degree. C. range; alternatively, a boiling point in the
70.degree. C. to 300.degree. C. range; alternatively, a boiling
point in the 80.degree. C. to 275.degree. C. range; alternatively,
a boiling point in the 80.degree. C. to 250.degree. C. range;
alternatively, a boiling point in the 100.degree. C. to 350.degree.
C. range; alternatively, a boiling point in the 125.degree. C. to
350.degree. C. range; alternatively, a boiling point in the
125.degree. C. to 300.degree. C. range; or alternatively, a boiling
point in the 150.degree. C. to 275.degree. C. range.
[0072] The alcohol compound can be miscible with or soluble in a
hydrocarbon solvent. For instance, the alcohol compound can be
miscible with or soluble in a hydrocarbon solvent comprising (or
consisting essentially of, or consisting of) a C.sub.3 to C.sub.10
hydrocarbon; alternatively, a C.sub.3 to C.sub.10 aliphatic
hydrocarbon; alternatively, a C.sub.3 to C.sub.8 aliphatic
hydrocarbon; or alternatively, a C.sub.4 to C.sub.8 aliphatic
hydrocarbon. The aliphatic hydrocarbon can be cyclic or acyclic,
and can be linear or branched, unless otherwise specified.
Illustrative aliphatic hydrocarbon solvents can include, but are
not limited to, propane, isobutane, n-butane, n-pentane,
isopentane, neopentane, n-hexane, heptane, octane, cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane, and the like,
including mixtures or combinations thereof.
[0073] Furthermore, the alcohol compound can be miscible with or
soluble in a hydrocarbon solvent comprising (or consisting
essentially of, or consisting of) a C.sub.6 to C.sub.10 aromatic
hydrocarbon or, alternatively, a C.sub.6 to C.sub.8 aromatic
hydrocarbon. Illustrative aromatic hydrocarbon solvents can
include, but are not limited to, benzene, toluene, xylene,
ethylbenzene, and the like, including mixtures or combinations
thereof.
[0074] In one embodiment, the alcohol compound can be miscible with
or soluble in propane, isobutane, n-butane, n-pentane, isopentane,
neopentane, n-hexane, heptane, octane, cyclohexane, cycloheptane,
methylcyclohexane, methylcycloheptane, benzene, toluene, xylene,
ethylbenzene, or a mixture thereof. In another embodiment, the
alcohol compound can be miscible with or soluble in propane,
cyclohexane, isobutane, n-butane, n-pentane, isopentane,
neopentane, n-hexane, or a mixture thereof. In yet another
embodiment, the alcohol compound can be miscible with or soluble in
propane; alternatively, isobutane; alternatively, n-butane;
alternatively, n-pentane; alternatively, isopentane; alternatively,
neopentane; alternatively, n-hexane; alternatively, heptane;
alternatively, octane; alternatively, cyclohexane; alternatively,
cycloheptane; alternatively, methylcyclohexane; alternatively,
methylcycloheptane; alternatively, benzene; alternatively, toluene;
alternatively, xylene; or alternatively, ethylbenzene.
[0075] Applicants also contemplate that the alcohol compound can be
miscible with or soluble in an ISOPAR.RTM. mixed aliphatic
hydrocarbon solvent, such as, for example, ISOPAR.RTM. C,
ISOPAR.RTM. E, ISOPAR.RTM. G, ISOPAR.RTM. H, ISOPAR.RTM. L,
ISOPAR.RTM. M, or a mixture thereof.
[0076] The alcohol compound, in certain embodiments, can be a
liquid (under atmospheric pressure) at a temperature in a range
from 50.degree. C. to 400.degree. C.; alternatively, in a range
from 50.degree. C. to 200.degree. C.; alternatively, in a range
from 50.degree. C. to 150.degree. C.; alternatively, in a range
from 50.degree. C. to 125.degree. C.; alternatively, in a range
from 75.degree. C. to 250.degree. C.; alternatively, in a range
from 75.degree. C. to 175.degree. C.; alternatively, in a range
from 75.degree. C. to 125.degree. C.; alternatively, in a range
from 60.degree. C. to 250.degree. C.; or alternatively, in a range
from 60.degree. C. to 150.degree. C.
Catalyst Systems
[0077] In some embodiments, the dual catalyst system can comprise a
first metallocene catalyst component and a second metallocene
catalyst component, while in other embodiments, the dual catalyst
system can comprise a first metallocene catalyst component, a
second metallocene catalyst component, an activator, and a
co-catalyst. The first metallocene catalyst component and the
second metallocene catalyst component independently can comprise,
for example, a transition metal (one or more than one) from Groups
IIIB-VIIIB of the Periodic Table of the Elements. In one
embodiment, the first metallocene catalyst component and the second
metallocene catalyst component independently can comprise a Group
III, IV, V, or VI transition metal, or a combination of two or more
transition metals. The first metallocene catalyst component and the
second metallocene catalyst component independently can comprise
chromium, titanium, zirconium, hafnium, vanadium, or a combination
thereof, or can comprise titanium, zirconium, hafnium, or a
combination thereof, in other embodiments. Accordingly, the first
metallocene catalyst component and the second metallocene catalyst
component independently can comprise titanium, or zirconium, or
hafnium, either singly or in combination.
[0078] In an embodiment, the first metallocene catalyst component
can produce the lower molecular weight component of the olefin
polymer, and the second metallocene catalyst component can produce
the higher molecular weight component of the olefin polymer. These
component terms are relative, are used in reference to each other,
and are not limited to the actual molecular weights of the
respective components. While not being limited thereto, the first
metallocene catalyst component can comprise an unbridged
metallocene; alternatively, an unbridged zirconium or hafnium based
metallocene compound, or an unbridged zirconium, hafnium, or
zirconium/hafnium based dinuclear metallocene compound;
alternatively, an unbridged zirconium or hafnium based metallocene
compound containing two cyclopentadienyl groups, two indenyl
groups, or a cyclopentadienyl and an indenyl group; alternatively,
an unbridged zirconium based metallocene compound containing two
cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl
and an indenyl group. Illustrative and non-limiting examples of
unbridged metallocene compounds (e.g., with zirconium or hafnium)
that can be employed in catalyst systems consistent with
embodiments of the present invention are described in U.S. Pat.
Nos. 7,199,073, 7,226,886, 7,312,283, and 7,619,047, the
disclosures of which are incorporated herein by reference in their
entirety.
[0079] In another embodiment, the first metallocene catalyst
component can produce the lower molecular weight component of the
olefin polymer, and the first metallocene catalyst component can
comprise zirconium, or alternatively, hafnium. Representative and
non-limiting examples of metallocene compounds that can be employed
as the first metallocene compound can include, but are not limited
to, the following (Ph=phenyl):
##STR00001## ##STR00002##
and the like, as well as combinations thereof
[0080] Moreover, the first metallocene catalyst component can
comprise an unbridged dinuclear metallocene such as those described
in U.S. Pat. Nos. 7,919,639 and 8,080,681, the disclosures of which
are incorporated herein by reference in their entirety. The first
metallocene catalyst component can comprise an unbridged zirconium,
hafnium, or zirconium/hafnium based dinuclear metallocene compound.
For example, the first metallocene catalyst component can comprise
an unbridged zirconium based homodinuclear metallocene compound, or
an unbridged hafnium based homodinuclear metallocene compound, or
an unbridged zirconium, hafnium, or zirconium/hafnium based
heterodinuclear metallocene compound (i.e., a dinuclear compound
with two hafniums, or two zirconiums, or one zirconium and one
hafnium). Representative and non-limiting dinuclear compounds can
include the following:
##STR00003## ##STR00004## ##STR00005##
and the like, as well as combinations thereof
[0081] While not being limited thereto, the second metallocene
catalyst component can comprise a bridged metallocene compound,
e.g., with titanium, zirconium, or hafnium, such as a bridged
zirconium based metallocene compound with a fluorenyl group, and
with no aryl groups on the bridging group, or a bridged zirconium
based metallocene compound with a cyclopentadienyl group and a
fluorenyl group, and with no aryl groups on the bridging group.
Such bridged metallocenes, in some embodiments, can contain an
alkenyl substituent (e.g., a terminal alkenyl) on the bridging
group, on a cyclopentadienyl-type group (e.g., a cyclopentadienyl
group, a fluorenyl group, etc.), or on the bridging group and the
cyclopentadienyl group. In another embodiment, the second
metallocene catalyst component can comprise a bridged zirconium or
hafnium based metallocene compound with a fluorenyl group, and an
aryl group on the bridging group; alternatively, a bridged
zirconium or hafnium based metallocene compound with a
cyclopentadienyl group and fluorenyl group, and an aryl group on
the bridging group; alternatively, a bridged zirconium based
metallocene compound with a fluorenyl group, and an aryl group on
the bridging group; or alternatively, a bridged hafnium based
metallocene compound with a fluorenyl group, and an aryl group on
the bridging group. In these and other embodiments, the aryl group
on the bridging group can be a phenyl group. Optionally, these
bridged metallocenes can contain an alkenyl substituent (e.g., a
terminal alkenyl) on the bridging group, on a cyclopentadienyl-type
group, or on both the bridging group and the cyclopentadienyl
group. Illustrative and non-limiting examples of bridged
metallocene compounds (e.g., with zirconium or hafnium) that can be
employed in catalyst systems consistent with embodiments of the
present invention are described in U.S. Pat. Nos. 7,026,494,
7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047, the
disclosures of which are incorporated herein by reference in their
entirety.
[0082] In another embodiment, the second metallocene catalyst
component can produce the higher molecular weight component of the
olefin polymer, and the second metallocene catalyst component can
comprise zirconium, hafnium, or both. Representative and
non-limiting examples of metallocene compounds that can be employed
as the second metallocene compound can include, but are not limited
to, the following (Ph=phenyl, Me=methyl, and t-Bu=tert-butyl):
##STR00006## ##STR00007## ##STR00008## ##STR00009##
and the like, as well as combinations thereof.
[0083] In some embodiments, the dual catalyst system can comprise
an activator. For example, the dual catalyst system can comprise a
first metallocene catalyst component, a second metallocene catalyst
component, and an activator, such as an activator-support, an
aluminoxane compound, an organoboron or organoborate compound, an
ionizing ionic compound, and the like, or any combination thereof.
The catalyst system can contain one or more than one activator.
[0084] In one embodiment, the dual catalyst system can comprise an
aluminoxane compound, an organoboron or organoborate compound, an
ionizing ionic compound, and the like, or a combination thereof.
Examples of such activators are disclosed in, for instance, U.S.
Pat. Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938,
5,919,983, and 8,114,946, the disclosures of which are incorporated
herein by reference in their entirety. In another embodiment, the
dual catalyst system can comprise an aluminoxane compound. In yet
another embodiment, the dual catalyst system can comprise an
organoboron or organoborate compound. In still another embodiment,
the dual catalyst system can comprise an ionizing ionic
compound.
[0085] In other embodiments, the dual catalyst system can comprise
an activator-support, for example, an activator-support comprising
a solid oxide treated with an electron-withdrawing anion. Examples
of such materials are disclosed in, for instance, U.S. Pat. Nos.
7,294,599 and 7,601,665, the disclosures of which are incorporated
herein by reference in their entirety.
[0086] The solid oxide used to produce the activator-support can
comprise oxygen and one or more elements from Groups 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, or
comprising oxygen and one or more elements from the lanthanide or
actinide elements (see e.g., Hawley's Condensed Chemical
Dictionary, 11.sup.th Ed., John Wiley & Sons, 1995; Cotton, F.
A., Wilkinson, G., Murillo, C. A., and Bochmann, M., Advanced
Inorganic Chemistry, 6.sup.th Ed., Wiley-Interscience, 1999). For
instance, the solid oxide can comprise oxygen and at least one
element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La,
Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr.
[0087] Accordingly, suitable examples of solid oxide materials that
can be used to form the activator-supports can include, but are not
limited to, Al.sub.2O.sub.3, B.sub.2O.sub.3, BeO, Bi.sub.2O.sub.3,
CdO, Co.sub.3O.sub.4, Cr.sub.2O.sub.3, CuO, Fe.sub.2O.sub.3,
Ga.sub.2O.sub.3, La.sub.2O.sub.3, Mn.sub.2O.sub.3, MoO.sub.3, NiO,
P.sub.2O.sub.5, Sb.sub.2O.sub.5, SiO.sub.2, SnO.sub.2, SrO,
ThO.sub.2, TiO.sub.2, V.sub.2O.sub.5, WO.sub.3, Y.sub.2O.sub.3,
ZnO, ZrO.sub.2, and the like, including mixed oxides thereof, and
combinations thereof. This includes co-gels or co-precipitates of
different solid oxide materials. The solid oxide can encompass
oxide materials such as alumina, "mixed oxides" thereof such as
silica-alumina, coatings of one oxide on another, and combinations
and mixtures thereof. The mixed oxides such as silica-alumina can
be single or multiple chemical phases with more than one metal
combined with oxygen to form the solid oxide. Examples of mixed
oxides that can be used to form an activator-support, either singly
or in combination, can include, but are not limited to,
silica-alumina, silica-titania, silica-zirconia, alumina-titania,
alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,
aluminophosphate-silica, titania-zirconia, and the like. The solid
oxide used herein also can encompass oxide materials such as
silica-coated alumina, as described in U.S. Pat. No. 7,884,163, the
disclosure of which is incorporated herein by reference in its
entirety.
[0088] Accordingly, in one embodiment, the solid oxide can comprise
silica, alumina, silica-alumina, silica-coated alumina, aluminum
phosphate, aluminophosphate, heteropolytungstate, titania,
zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or
any combination thereof. In another embodiment, the solid oxide can
comprise silica, alumina, titania, zirconia, magnesia, boria, zinc
oxide, any mixed oxide thereof, or any combination thereof. In yet
another embodiment, the solid oxide can comprise silica-alumina,
silica-coated alumina, silica-titania, silica-zirconia,
alumina-boria, or any combination thereof. In still another
embodiment, the solid oxide can comprise silica; alternatively,
alumina; alternatively, silica-alumina; or alternatively,
silica-coated alumina.
[0089] The silica-alumina which can be used typically can have an
alumina content from about 5 to about 95% by weight. In one
embodiment, the alumina content of the silica-alumina can be from
about 5 to about 50%, or from about 8% to about 30%, alumina by
weight. In another embodiment, high alumina content silica-alumina
materials can be employed, in which the alumina content of these
silica-alumina materials typically can range from about 60% to
about 90%, or from about 65% to about 80%, alumina by weight.
According to yet another embodiment, the solid oxide component can
comprise alumina without silica, and according to another
embodiment, the solid oxide component can comprise silica without
alumina. Moreover, as provided hereinabove, the solid oxide can
comprise a silica-coated alumina. The solid oxide can have any
suitable surface area, pore volume, and particle size, as would be
recognized by those of skill in the art.
[0090] The electron-withdrawing component used to treat the solid
oxide can be any component that increases the Lewis or Bronsted
acidity of the solid oxide upon treatment (as compared to the solid
oxide that is not treated with at least one electron-withdrawing
anion). According to one embodiment, the electron-withdrawing
component can be an electron-withdrawing anion derived from a salt,
an acid, or other compound, such as a volatile organic compound,
that serves as a source or precursor for that anion. Examples of
electron-withdrawing anions can include, but are not limited to,
sulfate, bisulfate, fluoride, chloride, bromide, iodide,
fluorosulfate, fluoroborate, phosphate, fluorophosphate,
trifluoroacetate, triflate, fluorozirconate, fluorotitanate,
phospho-tungstate, and the like, including mixtures and
combinations thereof. In addition, other ionic or non-ionic
compounds that serve as sources for these electron-withdrawing
anions also can be employed. It is contemplated that the
electron-withdrawing anion can be, or can comprise, fluoride,
chloride, bromide, phosphate, triflate, bisulfate, or sulfate, and
the like, or any combination thereof, in some embodiments provided
herein. In other embodiments, the electron-withdrawing anion can
comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide,
fluorosulfate, fluoroborate, phosphate, fluorophosphate,
trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and
the like, or combinations thereof.
[0091] In an embodiment, the dual catalyst system can comprise an
activator-support, and the activator-support can comprise fluorided
alumina, chlorided alumina, bromided alumina, sulfated alumina,
fluorided silica-alumina, chlorided silica-alumina, bromided
silica-alumina, sulfated silica-alumina, fluorided silica-zirconia,
chlorided silica-zirconia, bromided silica-zirconia, sulfated
silica-zirconia, fluorided silica-titania, fluorided silica-coated
alumina, sulfated silica-coated alumina, phosphated silica-coated
alumina, and the like, as well as any mixture or combination
thereof. In another embodiment, the dual catalyst system can
comprise an activator-support, and the activator-support can
comprise a fluorided solid oxide, a sulfated solid oxide, or a
combination thereof. In yet another embodiment, the dual catalyst
system can comprise an activator-support, and the activator-support
can comprise fluorided alumina, sulfated alumina, fluorided
silica-alumina, sulfated silica-alumina, fluorided silica-zirconia,
fluorided silica-coated alumina, sulfated silica-coated alumina,
and the like, as well as any mixture or combination thereof.
[0092] As described herein, the alcohol compound can be added to
the polymerization reactor system (e.g., into a polymerization
reactor) alone, with a carrier, with the dual catalyst system,
etc., and the amount of the alcohol compound added to the reactor
system is not particularly limited, so long as the amount of the
alcohol compound added to the reactor system is sufficient to
impact at least one of the MI, HLMI, Mw, and Mz of the olefin
polymer as described herein, and does not adversely impact the
catalyst activity or polymer production rate in a significant
manner (e.g., 20%+ reduction in catalyst activity, polymer
production rate, or both). Nonetheless, while not being limited
thereto, the amount of the alcohol compound added typically can be
in a range of the moles of hydroxyl (--OH) groups of the alcohol
compound to the weight (in grams) of the activator (e.g., an
activator-support comprising a solid oxide treated with an
electron-withdrawing anion) of from about 1:10,000 to about 1:10.
This range of ratios is based on the respective amounts of hydroxyl
groups of the alcohol compound and the weight of activator (e.g.,
activator-support) fed into the reactor system (e.g., into a
polymerization reactor). As a non-limiting example of a 1:1000
ratio, in a continuous polymerization reactor system, the total
amount of an activator, such as an activator-support, fed into the
reactor(s) per time interval can be "W" g/hour; thus, the amount of
the alcohol compound fed into the reactor(s) would be equal to
"0.001 W" moles/hour (moles of hydroxyl groups) for a 1:1000
ratio.
[0093] In some embodiments, this ratio (moles of hydroxyl groups of
the alcohol compound to weight of the activator, such as an
activator-support) can be in a range from about 1:10,000 to about
1:10, from about 1:5,000 to about 1:10, from about 1:2,500 to about
1:10, from about 1:10,000 to about 1:50, from about 1:5,000 to
about 1:50, from about 1:5,000 to about 1:100, from about 1:5,000
to about 1:250, or from about 1:5,000 to about 1:500. In particular
embodiments considered herein, the ratio can be in a range from
about 1:7,000 to about 1:100, from about to about 1:2,500 to about
1:250, from about 1:1,500 to about 1:250, from about 1:1,500 to
about 1:500, from about 1:2,000 to about 1:1,000, or from about
1:1,500 to about 1:1,000.
[0094] Commonly used polymerization co-catalysts which can be
utilized in the dual catalyst system can include, but are not
limited to, metal alkyl, or organometal, co-catalysts, with the
metal being, for example, aluminum. The dual catalyst systems
provided herein can comprise a co-catalyst, or a combination of
co-catalysts. While not being limited thereto, representative
aluminum compounds (e.g., organoaluminum compounds) can include
trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum
ethoxide, diethylaluminum chloride, and the like, as well as any
combination thereof. Thus, a dual catalyst system provided herein
can comprise a first metallocene catalyst component, a second
metallocene catalyst component, an activator, and a co-catalyst. In
an embodiment, the co-catalyst can comprise an organoaluminum
compound, such as triethylaluminum or triisobutylaluminum, while
the activator can comprise a fluorided solid oxide or a sulfated
solid oxide, representative examples of which can include fluorided
alumina, sulfated alumina, fluorided silica-alumina, sulfated
silica-alumina, fluorided silica-zirconia, fluorided silica-coated
alumina, sulfated silica-coated alumina, as well as any combination
thereof.
[0095] The amount of the alcohol compound added to the reactor
system, based on the amount of the co-catalyst, is not particularly
limited, so long as the amount of the alcohol compound added to the
reactor system is sufficient to impact at least one of the MI,
HLMI, Mw, and Mz of the olefin polymer as described herein, and
does not adversely impact the catalyst activity or polymer
production rate in a significant manner (e.g., 20%+ reduction in
catalyst activity, polymer production rate, or both). As one of
skill in the art would readily understand, an excess of the alcohol
compound, as compared to the co-catalyst component of the dual
catalyst system, can drastically reduce the catalyst activity and
polymer production rate and, eventually, can "kill" the reaction.
Accordingly, while not being limited thereto, the amount of the
alcohol compound added typically can be in a range of moles of
hydroxyl (--OH) groups of the alcohol compound to the moles of the
co-catalyst (e.g., an organoaluminum compound) from about 0.05:1 to
about 0.9:1. This molar ratio is based on the respective amounts of
hydroxyl groups of the alcohol compound and the co-catalyst fed
into the reactor system (e.g., into a polymerization reactor). As a
non-limiting example of a 0.5:1 molar ratio, in a continuous
polymerization reactor system, the amount of the co-catalyst
component (e.g., an organoaluminum compound) fed into the
reactor(s) per time interval can be "Z" moles/hour; thus, the
amount of the alcohol compound fed into the reactor(s) would be
equal to "0.5 Z" moles/hour (moles of hydroxyl groups) for a 0.5:1
molar ratio.
[0096] In some embodiments, the molar ratio (moles of hydroxyl
groups of the alcohol compound to moles of co-catalyst, such as
organoaluminum compounds) can be in a range from about 0.05:1 to
about 0.85:1, from about 0.1:1 to about 0.9:1, from about 0.1:1 to
about 0.85:1, from about 0.05:1 to about 0.8:1, from about 0.1:1 to
about 0.8:1, from about 0.05:1 to about 0.75:1, from about 0.1:1 to
about 0.75:1, from about 0.15:1 to about 0.85:1, or from about
0.15:1 to about 0.75:1. In particular embodiments considered
herein, the molar ratio can be in a range from about 0.2:1 to about
0.9:1, from about to about 0.2:1 to about 0.8:1, from about 0.2:1
to about 0.7:1, from about 0.2:1 to about 0.6:1, from about 0.1:1
to about 0.6:1, or from about 0.25:1 to about 0.75:1.
Olefin Monomers and Olefin Polymers
[0097] Olefin monomers contemplated herein typically include olefin
compounds having from 2 to 30 carbon atoms per molecule and having
at least one olefinic double bond. Homopolymerization processes
using a single olefin, such as ethylene, propylene, butene, hexene,
octene, and the like, are encompassed, as well as copolymerization,
terpolymerization, etc., reactions using an olefin monomer with at
least one different olefinic compound. For example, resultant
ethylene copolymers, terpolymers, etc., generally can contain a
major amount of ethylene (>50 mole percent) and a minor amount
of comonomer (<50 mole percent), though this is not a
requirement. Comonomers that can be copolymerized with ethylene
often can have from 3 to 20 carbon atoms, or from 3 to 10 carbon
atoms, in their molecular chain.
[0098] Acyclic, cyclic, polycyclic, terminal (.alpha.), internal,
linear, branched, substituted, unsubstituted, functionalized, and
non-functionalized olefins can be employed. For example, typical
unsaturated compounds that can be polymerized to produce olefin
polymers can include, but are not limited to, ethylene, propylene,
1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene,
2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,
2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene,
3-heptene, the four normal octenes (e.g., 1-octene), the four
normal nonenes, the five normal decenes, and the like, or mixtures
of two or more of these compounds. Cyclic and bicyclic olefins,
including but not limited to, cyclopentene, cyclohexene,
norbornylene, norbornadiene, and the like, also can be polymerized
as described herein. Styrene also can be employed as a monomer or
as a comonomer. In an embodiment, the olefin monomer can comprise a
C.sub.2-C.sub.20 olefin; alternatively, a C.sub.2-C.sub.20
.alpha.-olefin; alternatively, a C.sub.2-C.sub.12 olefin;
alternatively, a C.sub.2-C.sub.10 .alpha.-olefin; alternatively,
ethylene, propylene, 1-butene, 1-hexene, or 1-octene;
alternatively, ethylene or propylene; alternatively, ethylene; or
alternatively, propylene.
[0099] When a copolymer (or alternatively, a terpolymer) is
desired, the olefin monomer can be, for example, ethylene or
propylene, which is copolymerized with at least one comonomer
(e.g., a C.sub.2-C.sub.20 .alpha.-olefin, a C.sub.3-C.sub.20
.alpha.-olefin, etc.). According to one embodiment, the olefin
monomer in the polymerization process can be ethylene. In this
embodiment, examples of suitable olefin comonomers can include, but
are not limited to, propylene, 1-butene, 2-butene,
3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,
3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,
3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,
1-decene, styrene, and the like, or combinations thereof. According
to another embodiment, the comonomer can comprise an .alpha.-olefin
(e.g., a C.sub.3-C.sub.10 .alpha.-olefin), while in yet another
embodiment, the comonomer can comprise 1-butene, 1-pentene,
1-hexene, 1-octene, 1-decene, styrene, or any combination thereof.
For example, the comonomer can comprise 1-butene, 1-hexene,
1-octene, or a combination thereof.
[0100] Generally, the amount of comonomer introduced into a
polymerization reactor to produce the copolymer can be from about
0.01 to about 50 weight percent of the comonomer based on the total
weight of the monomer and comonomer. According to another
embodiment, the amount of comonomer introduced into a
polymerization reactor can be from about 0.01 to about 40 weight
percent comonomer based on the total weight of the monomer and
comonomer. In still another embodiment, the amount of comonomer
introduced into a polymerization reactor can be from about 0.1 to
about 35 weight percent comonomer based on the total weight of the
monomer and comonomer. Yet, in another embodiment, the amount of
comonomer introduced into a polymerization reactor can be from
about 0.5 to about 20 weight percent comonomer based on the total
weight of the monomer and comonomer.
[0101] While not intending to be bound by this theory, where
branched, substituted, or functionalized olefins are used as
reactants, it is believed that a steric hindrance can impede or
slow the polymerization reaction. Thus, branched or cyclic
portion(s) of the olefin removed somewhat from the carbon-carbon
double bond would not be expected to hinder the reaction in the way
that the same olefin substituents situated more proximate to the
carbon-carbon double bond might.
[0102] According to one embodiment, at least one monomer/reactant
can be ethylene, so the polymerization reaction can be a
homopolymerization involving only ethylene, or a copolymerization
with a different acyclic, cyclic, terminal, internal, linear,
branched, substituted, or unsubstituted olefin. In addition, the
methods disclosed herein intend for olefin to also encompass
diolefin compounds that include, but are not limited to,
1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, and the
like.
[0103] Olefin polymers encompassed herein can include any polymer
(or oligomer) produced from any olefin monomer (and optional
comonomer(s)) described herein. For example, the olefin polymer can
comprise an ethylene homopolymer, a propylene homopolymer, an
ethylene copolymer (e.g., ethylene/.alpha.-olefin,
ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), a
propylene copolymer, an ethylene terpolymer, a propylene
terpolymer, and the like, including combinations thereof. Moreover,
additional polymer components can be present in the olefin polymer,
in addition to the higher molecular weight component and the lower
molecular weight component. Accordingly, in one embodiment, the
olefin polymer can have a bimodal molecular weight distribution,
while in another embodiment, the olefin polymer can have a
multimodal molecular weight distribution. In yet another
embodiment, the olefin polymer can have a unimodal molecular weight
distribution.
Polymerization Reactor Systems
[0104] The disclosed methods and processes are intended for any
olefin polymerization process using various types of polymerization
reactors, polymerization reactor systems, and polymerization
reaction conditions. As used herein, "polymerization reactor"
includes any polymerization reactor capable of polymerizing olefin
monomers and comonomers (one or more than one comonomer) to produce
homopolymers, copolymers, terpolymers, and the like. The various
types of polymerization reactors include those that can be referred
to as a batch reactor, slurry reactor, gas-phase reactor, solution
reactor, high pressure reactor, tubular reactor, autoclave reactor,
and the like, or combinations thereof. Suitable polymerization
conditions are used for the various reactor types. Gas phase
reactors can comprise fluidized bed reactors or staged horizontal
reactors. Slurry reactors can comprise vertical or horizontal
loops. High pressure reactors can comprise autoclave or tubular
reactors. Reactor types can include batch or continuous processes.
Continuous processes can use intermittent or continuous product
discharge. Polymerization reactor systems and processes also can
include partial or full direct recycle of unreacted monomer,
unreacted comonomer, or diluent.
[0105] A polymerization reactor system can comprise a single
reactor or multiple reactors (2 reactors, more than 2 reactors,
etc.) of the same or different type. For instance, the
polymerization reactor system can comprise a slurry reactor, a
gas-phase reactor, a solution reactor, or a combination of two or
more of these reactors. Production of polymers in multiple reactors
can include several stages in at least two separate polymerization
reactors interconnected by a transfer device making it possible to
transfer the polymers resulting from the first polymerization
reactor into the second reactor. The desired polymerization
conditions in one of the reactors can be different from the
operating conditions of the other reactor(s). Alternatively,
polymerization in multiple reactors can include the manual transfer
of polymer from one reactor to subsequent reactors for continued
polymerization. Multiple reactor systems can include any
combination including, but not limited to, multiple loop reactors,
multiple gas phase reactors, a combination of loop and gas phase
reactors, multiple high pressure reactors, or a combination of high
pressure with loop or gas phase reactors. The multiple reactors can
be operated in series, in parallel, or both.
[0106] According to one embodiment, the polymerization reactor
system can comprise at least one loop slurry reactor comprising
vertical or horizontal loops. Monomer, diluent, catalyst, and
comonomer can be continuously fed to a loop reactor where
polymerization occurs. Generally, continuous processes can comprise
the continuous introduction of monomer/comonomer, a catalyst, and a
diluent into a polymerization reactor and the continuous removal
from this reactor of a suspension comprising polymer particles and
the diluent. Reactor effluent can be flashed to remove the solid
polymer from the liquids that comprise the diluent, monomer,
comonomer, etc. Various technologies can be used for this
separation step including, but not limited to, flashing that can
include any combination of heat addition and pressure reduction,
separation by cyclonic action in either a cyclone or hydrocyclone,
or separation by centrifugation.
[0107] A typical slurry polymerization process (also known as the
particle form process) is disclosed, for example, in U.S. Pat. Nos.
3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191,
and 6,833,415, each of which is incorporated herein by reference in
its entirety.
[0108] Suitable diluents used in slurry polymerization include, but
are not limited to, the monomer being polymerized and hydrocarbons
that are liquids under reaction conditions. Examples of suitable
diluents include, but are not limited to, hydrocarbons such as
propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane,
neopentane, and n-hexane. Some loop polymerization reactions can
occur under bulk conditions where no diluent is used. An example is
polymerization of propylene monomer as disclosed in U.S. Pat. No.
5,455,314, which is incorporated by reference herein in its
entirety.
[0109] According to yet another embodiment, the polymerization
reactor system can comprise at least one gas phase reactor (e.g., a
fluidized bed reactor). Such reactor systems can employ a
continuous recycle stream containing one or more monomers
continuously cycled through a fluidized bed in the presence of the
catalyst under polymerization conditions. A recycle stream can be
withdrawn from the fluidized bed and recycled back into the
reactor. Simultaneously, polymer product can be withdrawn from the
reactor and new or fresh monomer can be added to replace the
polymerized monomer. Such gas phase reactors can comprise a process
for multi-step gas-phase polymerization of olefins, in which
olefins are polymerized in the gaseous phase in at least two
independent gas-phase polymerization zones while feeding a
catalyst-containing polymer formed in a first polymerization zone
to a second polymerization zone. One type of gas phase reactor is
disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and 5,436,304,
each of which is incorporated by reference in its entirety
herein.
[0110] According to still another embodiment, the polymerization
reactor system can comprise a high pressure polymerization reactor,
e.g., can comprise a tubular reactor or an autoclave reactor.
Tubular reactors can have several zones where fresh monomer,
initiators, or catalysts are added. Monomer can be entrained in an
inert gaseous stream and introduced at one zone of the reactor.
Initiators, catalysts, catalyst components, etc., can be entrained
in a gaseous stream and introduced at another zone of the reactor.
The gas streams can be intermixed for polymerization. Heat and
pressure can be employed appropriately to obtain optimal
polymerization reaction conditions.
[0111] According to yet another embodiment, the polymerization
reactor system can comprise a solution polymerization reactor
wherein the monomer/comonomer are contacted with the catalyst
composition by suitable stirring or other means. A carrier
comprising an inert organic diluent or excess monomer can be
employed. If desired, the monomer/comonomer can be brought in the
vapor phase into contact with the catalytic reaction product, in
the presence or absence of liquid material. The polymerization zone
can be maintained at temperatures and pressures that will result in
the formation of a solution of the polymer in a reaction medium.
Agitation can be employed to obtain better temperature control and
to maintain uniform polymerization mixtures throughout the
polymerization zone. Adequate means are utilized for dissipating
the exothermic heat of polymerization.
[0112] The polymerization reactor system can further comprise any
combination of at least one raw material feed system, at least one
feed system for catalyst or catalyst components, and at least one
polymer recovery system. Suitable reactor systems can further
comprise systems for feedstock purification, catalyst storage and
preparation, extrusion, reactor cooling, polymer recovery,
fractionation, recycle, storage, loadout, laboratory analysis, and
process control. Depending upon the desired properties of the
olefin polymer, hydrogen can be added to the polymerization reactor
as needed (e.g., continuously, pulsed, etc.), and as discussed
hereinabove.
[0113] Polymerization conditions that can be controlled for
efficiency and to provide desired polymer properties can include
temperature, pressure, and the concentrations of various reactants.
Polymerization temperature can affect catalyst productivity,
polymer molecular weight, and molecular weight distribution. A
suitable polymerization temperature can be any temperature below
the de-polymerization temperature according to the Gibbs Free
energy equation. Typically, this includes from about 60.degree. C.
to about 280.degree. C., for example, or from about 60.degree. C.
to about 120.degree. C., depending upon the type of polymerization
reactor. In some reactor systems, the polymerization temperature
generally can be within a range from about 70.degree. C. to about
110.degree. C., or from about 75.degree. C. to about 95.degree.
C.
[0114] Suitable pressures will also vary according to the reactor
and polymerization type. The pressure for liquid phase
polymerizations in a loop reactor typically can be less than 1000
psig. The pressure for gas phase polymerization can be in the 200
to 500 psig range. High pressure polymerization in tubular or
autoclave reactors generally can be conducted at about 20,000 to
75,000 psig. Polymerization reactors also can be operated in a
supercritical region occurring at generally higher temperatures and
pressures. Operation above the critical point of a
pressure/temperature diagram (supercritical phase) can offer
advantages.
Examples
[0115] Embodiments of the invention are further illustrated by the
following examples, which are not to be construed in any way as
imposing limitations to the scope of this invention described
herein. Various other aspects, embodiments, modifications, and
equivalents thereof which, after reading the description herein,
can suggest themselves to one of ordinary skill in the art without
departing from the spirit of the present invention or the scope of
the appended claims.
[0116] Melt index (MI, g/10 min) was determined in accordance with
ASTM D1238 at 190.degree. C. with a 2,160 gram weight. High load
melt index (HLMI, g/10 min) was determined in accordance with ASTM
D1238 at 190.degree. C. with a 21,600 gram weight.
[0117] Molecular weights and molecular weight distributions were
obtained using a PL-GPC 220 (Polymer Labs, an Agilent Company)
system equipped with a IR4 detector (Polymer Char, Spain) and three
Styragel HMW-6E GPC columns (Waters, Mass.) running at 145.degree.
C. The flow rate of the mobile phase 1,2,4-trichlorobenzene (TCB)
containing 0.5 g/L 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1
mL/min, and polymer solution concentrations were in the range of
1.0-1.5 mg/mL, depending on the molecular weight. Sample
preparation was conducted at 150.degree. C. for nominally 4 hr with
occasional and gentle agitation, before the solutions were
transferred to sample vials for injection. The integral calibration
method was used to deduce molecular weights and molecular weight
distributions using a Chevron Phillips Chemicals Company's HDPE
polyethylene resin, MARLEX BHB5003, as the broad standard. The
integral table of the broad standard was pre-determined in a
separate experiment with SEC-MALS. Mn is the number-average
molecular weight, Mw is the weight-average molecular weight, Mz is
the z-average molecular weight, and Mp is the peak molecular
weight.
[0118] Sulfated alumina activator-supports were prepared as
follows. Bohemite was obtained from W.R. Grace & Company under
the designation "Alumina A" and having a surface area of about 300
m.sup.2/g and a pore volume of about 1.3 mL/g. This material was
obtained as a powder having an average particle size of about 100
microns. This material was impregnated to incipient wetness with an
aqueous solution of ammonium sulfate to equal about 15% sulfate.
This mixture was then placed in a flat pan and allowed to dry under
vacuum at approximately 110.degree. C. for about 16 hours. To
calcine the resultant powdered mixture, the material was fluidized
in a stream of dry air at about 550.degree. C. for about 6 hours.
Afterward, the sulfated alumina was collected and stored under dry
nitrogen, and was used without exposure to the atmosphere.
Examples 1-4
Impact of the Addition of Isopropyl Alcohol on the Melt Index and
Molecular Weight Parameters of an Ethylene/1-Hexene Copolymer
[0119] The polymerization experiments of Examples 1-4 were
conducted in a one-gallon (3.8-L) stainless steel reactor with 2 L
of isobutane. Metallocene solutions (nominal 1 mg/mL) of MET-A and
MET-B were prepared by dissolving 15 mg of the respective
metallocene in 15 mL of toluene. Metallocene compounds MET-A and
MET-B had the following structures:
##STR00010##
[0120] Approximately 2 mg of MET-A and 2 mg of MET-B (a 1:1 weight
ratio) were used in Examples 1-4, and the MET-A and MET-B
metallocene solutions were premixed before they were charged into
the reactor.
[0121] The polymerization experiments were performed as follows.
First, 0.6 mmol of triisobutylaluminum (TIBA), 300 mg of sulfated
alumina, and the premixed metallocene solution containing MET-A and
MET-B were added in that order through a charge port while slowly
venting isobutane vapor. The charge port was closed and 2 L of
isobutane were added. The contents of the reactor were stirred and
heated to the desired polymerization reaction temperature of
95.degree. C., and ethylene and isopropyl alcohol were then
introduced into the reactor with 10 g of 1-hexene and hydrogen
(H.sub.2) at 300 ppm by weight of the ethylene. Ethylene and
hydrogen were fed on demand at the specified weight ratio to
maintain the target pressure of 420 psig pressure for the 45 minute
length of each polymerization experiment. The reactor was
maintained at the desired reaction temperature throughout the
experiment by an automated heating-cooling system.
[0122] Table I summarizes the amount of isopropyl alcohol added,
the amount of polymer produced, and the melt flow and molecular
weight parameters for the polymers of Examples 1-4. As shown in
Table I, and unexpectedly, the addition of isopropyl alcohol
decreased the MI and the HLMI, and increased the Mw and Mz of the
polymer. Moreover, the addition of isopropyl alcohol decreased the
Mz/Mw ratio of the polymer. Furthermore, and quite surprisingly,
the addition of isopropyl alcohol did not significantly impact the
amount of polymer produced (or the catalyst activity).
[0123] The impact of isopropyl alcohol addition on the molecular
weight distributions (amount of polymer versus logarithm of
molecular weight) of the polymers of Examples 1-4 is illustrated
graphically in the FIGURE. As shown in the FIGURE, and
unexpectedly, the addition of isopropyl alcohol increased the
weight ratio of the higher molecular weight (HMW) component to the
lower molecular weight (LMW) component; relatively more higher
molecular weight material was produced. Moreover, the peak
molecular weight of the lower molecular weight component and the
peak molecular weight of the higher molecular weight component were
not substantially affected by isopropyl alcohol addition.
TABLE-US-00001 TABLE I Summary of Examples 1-4. Example 1 2 3 4
Isopropyl alcohol (mmol) 0 0.2 0.33 0.46 PE Produced (g) 207 238
231 203 MI (g/10 min) 0.07 0 0 0 HLMI (g/10 min) 16.6 6.5 3.4 1.5
HLMI/MI 236 -- -- -- Mn/1000 (g/mol) 11.7 12.4 11.8 19.0 Mw/1000
(g/mol) 249 288 316 363 Mz/1000 (g/mol) 1,135 1,346 1,369 1,439
Mp/1000 (g/mol) 20.5 19.5 474 452 Mw/Mn 21.3 23.2 26.8 19.2 Mz/Mw
4.6 4.7 4.3 4.0
[0124] The invention is described above with reference to numerous
aspects and embodiments, and specific examples. Many variations
will suggest themselves to those skilled in the art in light of the
above detailed description. All such obvious variations are within
the full intended scope of the appended claims. Other embodiments
of the invention can include, but are not limited to, the following
(embodiments are described as "comprising" but, alternatively, can
"consist essentially of" or "consist of"):
Embodiment 1
[0125] A method of controlling a polymerization reaction in a
polymerization reactor system, the method comprising:
[0126] (i) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in the polymerization reactor
system under polymerization conditions to produce an olefin
polymer,
[0127] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0128] (ii) introducing an amount of an alcohol compound into the
polymerization reactor system to reduce a melt index parameter
(e.g., MI, HLMI, etc.), to increase a molecular weight parameter
(e.g., Mw, Mz, etc.), or to reduce a melt index parameter and
increase a molecular weight parameter, of the olefin polymer.
Embodiment 2
[0129] A process for producing an olefin polymer with a target melt
index parameter (e.g., MI, HLMI, etc.), a target molecular weight
parameter (e.g., Mw, Mz, etc.), or a target melt index parameter
and a target molecular weight parameter, the process
comprising:
[0130] (a) contacting a dual catalyst system with an olefin monomer
and an optional olefin comonomer in a polymerization reactor system
under polymerization conditions,
[0131] wherein the dual catalyst system comprises a first
metallocene catalyst component, a second metallocene catalyst
component, an activator, and a co-catalyst; and
[0132] (b) controlling an amount of an alcohol compound introduced
into the polymerization reactor system to produce the olefin
polymer with the target melt index parameter (e.g., MI, HLMI,
etc.), the target molecular weight parameter (e.g., Mw, Mz, etc.),
or the target melt index parameter and the target molecular weight
parameter.
Embodiment 3
[0133] The method or process defined in embodiment 1 or 2, wherein
the alcohol compound comprises any alcohol compound disclosed
herein, e.g., a mono-ol, a diol, a triol, a polyol, etc., as well
as combinations thereof.
Embodiment 4
[0134] The method or process defined in any one of embodiments 1-3,
wherein the alcohol compound comprises a hydrocarbyl alcohol, e.g.,
an alkyl alcohol, a cycloalkyl alcohol, an aryl alcohol, an
arylalkyl alcohol, etc., as well as combinations thereof
Embodiment 5
[0135] The method or process defined in any one of embodiments 1-4,
wherein the alcohol compound comprises a C.sub.1 to C.sub.32
alcohol, e.g., a C.sub.1 to C.sub.18 alcohol, a C.sub.1 to C.sub.8
alcohol, a C.sub.1 to C.sub.4 alcohol, etc.
Embodiment 6
[0136] The method or process defined in any one of embodiments 1-3,
wherein the alcohol compound comprises any mono-ol disclosed
herein, e.g., methanol, ethanol, propanol (e.g., isopropanol,
n-propanol), butanol (e.g., n-butanol, isobutanol), pentanol,
hexanol, heptanol, octanol, decanol, hexadecanol, cyclohexanol,
phenol, benzyl alcohol, etc., as well as combinations thereof.
Embodiment 7
[0137] The method or process defined in any one of embodiments 1-3,
wherein the alcohol compound comprises any diol disclosed herein,
e.g., methanediol, ethylene glycol, propylene glycol, butanediol
(e.g., 1,4-butanediol), pentanediol, octanediol, bisphenol A, etc.,
as well as combinations thereof.
Embodiment 8
[0138] The method or process defined in any one of embodiments 1-3,
wherein the alcohol compound comprises any triol disclosed herein,
e.g., glycerol, benzenetriol, etc., as well as combinations
thereof
Embodiment 9
[0139] The method or process defined in any one of embodiments 1-3,
wherein the alcohol compound comprises any polyol disclosed herein,
e.g., erythritol, xylitol, mannitol, etc., as well as combinations
thereof.
Embodiment 10
[0140] The method or process defined in any one of embodiments 1-9,
wherein the alcohol compound has a boiling point in any range
disclosed herein, e.g., at least 60.degree. C., at least
100.degree. C., in range from 60.degree. C. to 400.degree. C., in a
range from 100.degree. C. to 350.degree. C., etc.
Embodiment 11
[0141] The method or process defined in any one of embodiments
1-10, wherein the alcohol compound is a liquid at a temperature in
any range disclosed herein, e.g., from 50.degree. C. to 200.degree.
C., from 50.degree. C. to 150.degree. C., from 75.degree. C. to
250.degree. C., from 75.degree. C. to 175.degree. C., etc.
Embodiment 12
[0142] The method or process defined in any one of embodiments
1-12, wherein the alcohol compound is miscible with or soluble in
any C.sub.3 to C.sub.10 hydrocarbon solvent disclosed herein, e.g.,
propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane,
neopentane, n-hexane, benzene, etc., as well as mixtures
thereof
Embodiment 13
[0143] The method or process defined in any one of embodiments
1-12, wherein the catalyst system comprises any (one or more) first
metallocene catalyst component, any (one or more) second
metallocene catalyst component, any (one or more) activator, and
any (one or more) co-catalyst disclosed herein.
Embodiment 14
[0144] The method or process defined in any one of embodiments
1-13, wherein the activator comprises an aluminoxane compound.
Embodiment 15
[0145] The method or process defined in any one of embodiments
1-13, wherein the activator comprises an organoboron or
organoborate compound.
Embodiment 16
[0146] The method or process defined in any one of embodiments
1-13, wherein the activator comprises an ionizing ionic
compound.
Embodiment 17
[0147] The method or process defined in any one of embodiments
1-13, wherein the activator comprises an activator-support
comprising a solid oxide treated with an electron-withdrawing
anion, for example, an activator-support comprising any solid oxide
treated with any electron-withdrawing anion disclosed herein.
Embodiment 18
[0148] The method or process defined in embodiment 17, wherein the
activator-support comprises a fluorided solid oxide, a sulfated
solid oxide, or a combination thereof
Embodiment 19
[0149] The method or process defined in embodiment 17, wherein the
solid oxide comprises silica, alumina, silica-alumina,
silica-coated alumina, aluminum phosphate, aluminophosphate,
heteropolytungstate, titania, zirconia, magnesia, boria, zinc
oxide, a mixed oxide thereof, or any mixture thereof; and the
electron-withdrawing anion comprises sulfate, bisulfate, fluoride,
chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,
fluorophosphate, trifluoroacetate, triflate, fluorozirconate,
fluorotitanate, phospho-tungstate, or any combination thereof.
Embodiment 20
[0150] The method or process defined in embodiment 17, wherein the
activator-support comprises fluorided alumina, chlorided alumina,
bromided alumina, sulfated alumina, fluorided silica-alumina,
chlorided silica-alumina, bromided silica-alumina, sulfated
silica-alumina, fluorided silica-zirconia, chlorided
silica-zirconia, bromided silica-zirconia, sulfated
silica-zirconia, fluorided silica-titania, fluorided silica-coated
alumina, sulfated silica-coated alumina, phosphated silica-coated
alumina, or any combination thereof.
Embodiment 21
[0151] The method or process defined in embodiment 17, wherein the
activator-support comprises fluorided alumina, sulfated alumina,
fluorided silica-alumina, sulfated silica-alumina, fluorided
silica-zirconia, fluorided silica-coated alumina, sulfated
silica-coated alumina, or any combination thereof.
Embodiment 22
[0152] The method or process defined in any one of embodiments
1-21, wherein the amount of the alcohol compound introduced into
the polymerization reactor system is in any range of molar ratios
disclosed herein, based on the moles of hydroxyl (--OH) groups of
the alcohol compound to the total moles of the first metallocene
catalyst component and the second metallocene catalyst component,
e.g., from about 10:1 to about 1000:1, from about 20:1 to about
500:1, from about 25:1 to about 100:1, etc.
Embodiment 23
[0153] The method or process defined in any one of embodiments
1-22, wherein the amount of the alcohol compound introduced into
the polymerization reactor system is in any range of ratios
disclosed herein, based on the moles of hydroxyl (--OH) groups of
the alcohol compound to the weight of the activator in grams, e.g.,
from about 1:10,000 to about 1:10, from about 1:5,000 to about
1:100, from about 1:1,500 to about 1:500, etc.
Embodiment 24
[0154] The method or process defined in any one of embodiments
1-23, wherein the co-catalyst comprises any organoaluminum compound
disclosed herein.
Embodiment 25
[0155] The method or process defined in embodiment 24, wherein the
organoaluminum compound comprises trimethylaluminum,
triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,
triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,
diisobutylaluminum hydride, diethylaluminum ethoxide,
diethylaluminum chloride, or any combination thereof.
Embodiment 26
[0156] The method or process defined in embodiment 24 or 25,
wherein the organoaluminum compound comprises triethylaluminum.
Embodiment 27
[0157] The method or process defined in embodiment 24 or 25,
wherein the organoaluminum compound comprises
triisobutylaluminum.
Embodiment 28
[0158] The method or process defined in any one of embodiments
24-27, wherein the activator comprises a fluorided solid oxide, a
sulfated solid oxide, or a combination thereof
Embodiment 29
[0159] The method or process defined in any one of embodiments
24-28, wherein the activator comprises fluorided alumina, sulfated
alumina, fluorided silica-alumina, sulfated silica-alumina,
fluorided silica-zirconia, fluorided silica-coated alumina,
sulfated silica-coated alumina, or any combination thereof.
Embodiment 30
[0160] The method or process defined in any one of embodiments
1-29, wherein the amount of the alcohol compound introduced into
the polymerization reactor system is in any range of molar ratios
disclosed herein, based on the moles of hydroxyl (--OH) groups of
the alcohol compound to the moles of the co-catalyst, e.g., from
about 0.05:1 to about 0.9:1, from about 0.1:1 to about 0.8:1, from
about 0.2:1 to about 0.7:1, etc.
Embodiment 31
[0161] The method or process defined in any one of embodiments
1-30, wherein the polymerization reactor system comprises a batch
reactor, a slurry reactor, a gas-phase reactor, a solution reactor,
a high pressure reactor, a tubular reactor, an autoclave reactor,
or a combination thereof
Embodiment 32
[0162] The method or process defined in any one of embodiments
1-31, wherein the polymerization reactor system comprises a slurry
reactor, a gas-phase reactor, a solution reactor, or a combination
thereof
Embodiment 33
[0163] The method or process defined in any one of embodiments
1-32, wherein the polymerization reactor system comprises a loop
slurry reactor.
Embodiment 34
[0164] The method or process defined in any one of embodiments
1-33, wherein the polymerization reactor system comprises a single
reactor.
Embodiment 35
[0165] The method or process defined in any one of embodiments
1-33, wherein the polymerization reactor system comprises 2
reactors.
Embodiment 36
[0166] The method or process defined in any one of embodiments
1-33, wherein the polymerization reactor system comprises more than
2 reactors.
Embodiment 37
[0167] The method or process defined in any one of embodiments
1-36, wherein the olefin monomer comprises a C.sub.2-C.sub.20
olefin.
Embodiment 38
[0168] The method or process defined in any one of embodiments
1-37, wherein the olefin monomer and the optional olefin comonomer
independently comprise a C.sub.2-C.sub.20 alpha-olefin.
Embodiment 39
[0169] The method or process defined in any one of embodiments
1-38, wherein the olefin monomer comprises ethylene.
Embodiment 40
[0170] The method or process defined in any one of embodiments
1-39, wherein the catalyst system is contacted with ethylene and a
C.sub.3-C.sub.10 alpha-olefin comonomer.
Embodiment 41
[0171] The method or process defined in any one of embodiments
1-40, wherein the catalyst system is contacted with ethylene and a
comonomer selected from 1-butene, 1-hexene, 1-octene, or a mixture
thereof
Embodiment 42
[0172] The method or process defined in any one of embodiments
1-41, wherein the olefin polymer in step (ii) or step (b) (or both)
has a multimodal molecular weight distribution.
Embodiment 43
[0173] The method or process defined in any one of embodiments
1-41, wherein the olefin polymer in step (ii) or step (b) (or both)
has a bimodal molecular weight distribution.
Embodiment 44
[0174] The method or process defined in any one of embodiments
1-41, wherein the olefin polymer in step (ii) or step (b) (or both)
has a unimodal molecular weight distribution.
Embodiment 45
[0175] The method or process defined in any one of embodiments
1-44, wherein the melt index (MI) of the olefin polymer in step
(ii) or step (b) (or both) is in any range disclosed herein, e.g.,
from 0 to about 25 g/10 min, from 0 to about 1 g/10 min, from 0 to
about 0.5 g/10 min, etc.
Embodiment 46
[0176] The method or process defined in any one of embodiments
1-45, wherein the high load melt index (HLMI) of the olefin polymer
in step (ii) or step (b) (or both) is in any range disclosed
herein, e.g., from 0 to about 100 g/10 min, from about 0.1 to about
50 g/10 min, from about 0.5 to about 25 g/10 min, etc.
Embodiment 47
[0177] The method or process defined in any one of embodiments
1-46, wherein the number-average molecular weight (Mn) of the
olefin polymer in step (ii) or step (b) (or both) is in any range
disclosed herein, e.g., from about 5,000 to about 40,000 g/mol,
from about 6,000 to about 25,000 g/mol, from about 9,000 to about
22,000 g/mol, etc.
Embodiment 48
[0178] The method or process defined in any one of embodiments
1-47, wherein the weight-average molecular weight (Mw) of the
olefin polymer in step (ii) or step (b) (or both) is in any range
disclosed herein, e.g., from about 100,000 to about 600,000 g/mol,
from about 200,000 to about 500,000 g/mol, or from about 225,000 to
about 400,000 g/mol.
Embodiment 49
[0179] The method or process defined in any one of embodiments
1-48, wherein the z-average molecular weight (Mz) of the olefin
polymer in step (ii) or step (b) (or both) is in any range
disclosed herein, e.g., from about 700,000 to about 3,000,000
g/mol, from about 800,000 to about 2,500,000 g/mol, or from about
1,000,000 to about 2,000,000 g/mol.
Embodiment 50
[0180] The method or process defined in any one of embodiments
1-49, wherein the Mw/Mn ratio of the olefin polymer in step (ii) or
step (b) (or both) is in any range disclosed herein, e.g., from
about 10 to about 40, from about 12 to about 35, from about 15 to
about 35, from about 15 to about 30, etc.
Embodiment 51
[0181] The method or process defined in any one of embodiments
1-50, wherein the Mz/Mw ratio of the olefin polymer in step (ii) or
step (b) (or both) is in any range disclosed herein, e.g., from
about 3 to about 7, from about 3.5 to about 7, from about 3.5 to
about 6, from about 3.8 to about 5.5, etc.
Embodiment 52
[0182] The method or process defined in any one of embodiments
1-51, wherein the olefin polymer is an ethylene/1-butene copolymer,
an ethylene/1-hexene copolymer, or an ethylene/1-octene
copolymer.
Embodiment 53
[0183] The method or process defined in any one of embodiments
1-52, wherein the olefin polymer is an ethylene/1-hexene
copolymer.
Embodiment 54
[0184] The method or process defined in any one of embodiments
1-53, wherein the first metallocene catalyst component and the
second metallocene catalyst component independently comprise
chromium, vanadium, titanium, zirconium, hafnium, or a combination
thereof
Embodiment 55
[0185] The method or process defined in any one of embodiments
1-54, wherein the first metallocene catalyst component and the
second metallocene catalyst component independently comprise
titanium, zirconium, hafnium, or a combination thereof.
Embodiment 56
[0186] The method or process defined in any one of embodiments
1-55, wherein the first metallocene catalyst component comprises
any first metallocene catalyst component disclosed herein, e.g., an
unbridged metallocene compound, an unbridged dinuclear metallocene
compound, etc.
Embodiment 57
[0187] The method or process defined in any one of embodiments
1-56, wherein the first metallocene catalyst component comprises
zirconium.
Embodiment 58
[0188] The method or process defined in any one of embodiments
1-57, wherein the second metallocene catalyst component comprises
any second metallocene catalyst component disclosed herein, e.g., a
bridged metallocene compound, etc.
Embodiment 59
[0189] The method or process defined in any one of embodiments
1-58, wherein the second metallocene catalyst component comprises
zirconium, hafnium, or both.
Embodiment 60
[0190] The method or process defined in any one of embodiments
1-59, wherein a weight ratio of the first metallocene catalyst
component to the second metallocene catalyst component is
substantially constant, for example, for a particular polymer
grade.
Embodiment 61
[0191] The method or process defined in any one of embodiments
1-59, further comprising a step of adjusting a weight ratio of the
first metallocene catalyst component to the second metallocene
catalyst component.
Embodiment 62
[0192] The method or process defined in any one of embodiments
1-61, wherein the polymerization conditions comprise a
polymerization reaction temperature in a range from about
60.degree. C. to about 120.degree. C. and a reaction pressure in a
range from about 200 to about 1000 psig (about 1.4 to about 6.9
MPa).
Embodiment 63
[0193] The method or process defined in any one of embodiments
1-62, wherein the polymerization conditions are substantially
constant, for example, for a particular polymer grade.
Embodiment 64
[0194] The method or process defined in any one of embodiments
1-62, further comprising a step of adjusting at least one
polymerization condition, e.g., temperature, pressure, residence
time, etc.
Embodiment 65
[0195] The method or process defined in any one of embodiments
1-64, wherein no hydrogen is added to the polymerization reactor
system.
Embodiment 66
[0196] The method or process defined in any one of embodiments
1-64, wherein hydrogen is added to the polymerization reactor
system, and the hydrogen addition is substantially constant, for
example, for a particular polymer grade.
Embodiment 67
[0197] The method or process defined in any one of embodiments
1-64, further comprising a step of adding hydrogen to the
polymerization reactor system to adjust the Mw or Mz (or Mw and Mz)
of the polymer.
Embodiment 68
[0198] The method or process defined in any one of embodiments
1-64, further comprising a step of adding hydrogen to the
polymerization reactor system to adjust the MI or HLMI (or MI and
HLMI) of the polymer.
Embodiment 69
[0199] The method or process defined in any one of embodiments
66-68, wherein the step of adding hydrogen decreases the Mw,
decreases the Mz, increases the MI, or increases the HLMI of the
polymer, as well as any combination thereof.
Embodiment 70
[0200] The method or process defined in any one of embodiments
1-69, further comprising the steps of determining (or measuring)
the MI, and adjusting the amount of the alcohol compound introduced
into the polymerization reactor system based on the difference
between the measured MI and the target MI.
Embodiment 71
[0201] The method or process defined in any one of embodiments
1-70, further comprising the steps of determining (or measuring)
the HLMI, and adjusting the amount of the alcohol compound
introduced into the polymerization reactor system based on the
difference between the measured HLMI and the target HLMI.
Embodiment 72
[0202] The method or process defined in any one of embodiments
1-71, further comprising the steps of determining (or measuring)
the Mw, and adjusting the amount of the alcohol compound introduced
into the polymerization reactor system based on the difference
between the measured Mw and the target Mw.
Embodiment 73
[0203] The method or process defined in any one of embodiments
1-72, further comprising the steps of determining (or measuring)
the Mz, and adjusting the amount of the alcohol compound introduced
into the polymerization reactor system based on the difference
between the measured Mz and the target Mz.
Embodiment 74
[0204] The method or process defined in any one of embodiments
1-73, wherein the olefin polymer comprises a higher molecular
weight component and a lower molecular weight component.
Embodiment 75
[0205] The method or process defined in embodiment 74, wherein
introducing the alcohol compound into the polymerization reactor
system increases the weight ratio of the higher molecular weight
component to the lower molecular weight component.
Embodiment 76
[0206] The method or process defined in embodiment 74 or 75,
wherein introducing the alcohol compound into the polymerization
reactor system has substantially no effect on the peak molecular
weight of the lower molecular weight component.
Embodiment 77
[0207] The method or process defined in any one of embodiments
74-76, wherein introducing the alcohol compound into the
polymerization reactor system has substantially no effect on the
peak molecular weight of the higher molecular weight component.
Embodiment 78
[0208] The method or process defined in any one of embodiments
74-77, wherein the first metallocene catalyst component produces
the lower molecular weight component.
Embodiment 79
[0209] The method or process defined in any one of embodiments
74-78, wherein the second metallocene catalyst component produces
the higher molecular weight component.
Embodiment 80
[0210] The method or process defined in any one of embodiments
1-79, wherein the alcohol compound is introduced into the
polymerization reactor system continuously.
Embodiment 81
[0211] The method or process defined in any one of embodiments
1-79, wherein the alcohol compound is introduced into the
polymerization reactor system periodically.
Embodiment 82
[0212] The method or process defined in any one of embodiments
1-81, wherein the weight ratio of the first metallocene catalyst
component to the second metallocene catalyst component is in any
range of weight ratios disclosed herein, e.g., from about 1:100 to
about 100:1, from about 1:5 to about 5:1, from about 1:2 to about
2:1, etc.
Embodiment 83
[0213] The method or process defined in any one of embodiments
1-82, wherein introducing the alcohol compound into the
polymerization reactor system has substantially no effect on the
catalyst activity of the dual catalyst system (or substantially no
effect on the production rate of the olefin polymer).
Embodiment 84
[0214] The method or process defined in any one of embodiments
1-83, wherein the MI of the olefin polymer decreases as the amount
of the alcohol compound added to the polymerization reactor system
increases.
Embodiment 85
[0215] The method or process defined in any one of embodiments
1-84, wherein the HLMI of the olefin polymer decreases as the
amount of the alcohol compound added to the polymerization reactor
system increases.
Embodiment 86
[0216] The method or process defined in any one of embodiments
1-85, wherein the Mw of the olefin polymer increases as the amount
of the alcohol compound added to the polymerization reactor system
increases.
Embodiment 87
[0217] The method or process defined in any one of embodiments
1-86, wherein the Mz of the olefin polymer increases as the amount
of the alcohol compound added to the polymerization reactor system
increases.
Embodiment 88
[0218] The method or process defined in any one of embodiments
1-87, wherein the Mz/Mw ratio of the olefin polymer decreases as
the amount of the alcohol compound added to the polymerization
reactor system increases.
Embodiment 89
[0219] The method or process defined in any one of embodiments
1-88, wherein introducing the alcohol compound into the
polymerization reactor system has substantially no effect on the Mn
of the olefin polymer.
* * * * *